Substrate with multilayer reflective film, mask blank, transfer mask and method of manufacturing semiconductor device

ABSTRACT

A substrate with a multilayer reflective film capable of facilitating the discovery of contaminants, scratches and other critical defects by inhibiting the detection of pseudo defects attributable to surface roughness of a substrate or film in a defect inspection using a highly sensitive defect inspection apparatus. 
     The substrate with a multilayer reflective film has a multilayer reflective film obtained by alternately laminating a high refractive index layer and a low refractive index layer on a main surface of a mask blank substrate used in lithography, wherein an integrated value I of the power spectrum density (PSD) at a spatial frequency of 1 μm −1  to 10 μm −1  of the surface of the substrate with a multilayer reflective film, obtained by measuring a region measuring 3 μm×3 μm with an atomic force microscope, is not more than 180×10 −3  nm 3 , and the maximum value of the power spectrum density (PSD) at a spatial frequency of 1 μm −1  to 10 μm −1  is not more than 50 nm 4 .

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No.PCT/JP2014/075379 filed Sep. 25, 2014, claiming priority based onJapanese Patent Application No. 2013-202493 filed Sep. 27, 2013, thecontents of all of which are incorporated herein by reference in theirentirety.

TECHNICAL FIELD

The present invention relates to a substrate with a multilayerreflective film, which is able to facilitate the discovery ofcontaminants or scratches and other critical defects by inhibitingpseudo defects attributable to surface roughness of a substrate or filmin a defect inspection using a highly sensitive defect inspectionapparatus, a mask blank, a transfer mask and a method of manufacturing asemiconductor device.

BACKGROUND ART

Accompanying the increasingly higher levels of integration ofsemiconductor devices in the semiconductor industry in recent years,there is a need for fine patterns that exceed the transfer limitationsof conventional photolithographic methods using ultraviolet light.Extreme ultraviolet (EUV) lithography is considered to be promising asan exposure technology that uses EUV light to enable the formation ofsuch fine patterns. Here, EUV light refers to light in the wavelengthband of the soft X-ray region or vacuum ultraviolet region, and morespecifically, light having a wavelength of about 0.2 nm to 100 nm.Reflective masks have been proposed as transfer masks for use in EUVlithography. Such reflective masks have a multilayer reflective filmthat reflects exposure light funned on a substrate, and an absorber filmthat absorbs exposure light formed in a pattern on the multilayerreflective film.

The reflective mask is fabricated from a substrate, a multilayerreflective film formed on the substrate, and a reflective mask blankhaving an absorber film formed on the multilayer reflective film, byforming an absorber film pattern by photolithography and the like.

As described above, due to the growing demand for miniaturization in thelithography process, significant problems are being encountered in thelithography process. One of these is the problem relating to defectinformation of mask blank substrates and substrates with a multilayerreflective film and the like used in the lithography process.

Mask blank substrates are being required to have even higher smoothnessfrom the viewpoints of improving defect quality accompanying theminiaturization of patterns in recent years and the optical propertiesrequired of transfer masks.

In addition, substrates with a multilayer reflective film are also beingrequired to have even higher smoothness from the viewpoints of improvingdefect quality accompanying the miniaturization of patterns in recentyears and the optical properties required of transfer masks. Multilayerreflective films are formed by alternately laminating layers having ahigh refractive index and layers having a low refractive index on thesurface of a mask blank substrate. Each of these layers is typicallyformed by sputtering using sputtering targets composed of the materialsthat form these layers.

Ion beam sputtering is preferably carried out as the sputtering methodfrom the viewpoint of being resistant to contamination by impuritiespresent in the multilayer reflective film as a result of not requiringthe generation of plasma by electrical discharge, and having anindependent ion source thereby making setting of conditionscomparatively easy. In the case of using ion beam sputtering, from theviewpoint of the smoothness and surface uniformity of each layer formed,the high refractive index layer and low refractive index layer aredeposited by allowing sputtered particles to reach the target at a largeangle with respect to the normal (line perpendicular to a main surfaceof the mask blank substrate) of a main surface of the mask blanksubstrate, or in other words, at an angle diagonal or nearly parallel toa main surface of the substrate.

Patent Literature 1 describes a technology for manufacturing a substratewith a multilayer reflective film using such a method in which, whendepositing a multilayer reflective film of a reflective mask blank forEUV lithography on a substrate, ion beam sputtering is carried out bymaintaining the absolute value of an angle α formed between the normalof the substrate and sputtered particles entering the substrate suchthat 35 degrees≦α≦80 degrees while rotating the substrate about thecentral axis thereof.

PRIOR ART LITERATURE Patent Literature

Patent Literature 1: JP 2009-510711A

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

Accompanying the rapid pace of pattern miniaturization in lithographyusing EUV light, the defect size of reflective masks in the form of EUVmasks is becoming increasingly smaller year by year. The inspectionlight source wavelengths used during defect inspections in order todiscover such fine defects are approaching the light source wavelengthof the exposure light.

For example, highly sensitive defect inspection apparatuses employing aninspection wavelength of 266 nm (such as the “MAGICS M7360”Mask/Substrate/Blank Defect Inspection Apparatus for EUV Exposuremanufactured by Lasertec Corp.), an inspection wavelength of 193 nm(such as the “Teron 610” of “Teron 600 Series” of Reticule, OpticalMask/Blank and UV Mask/Blank Defect Inspection Apparatuses manufacturedby KLA-Tencor Corp.), or an inspection wavelength of 13.5 nm, are beingused or proposed increasingly frequently as defect inspectionapparatuses of EUV masks and masters thereof in the form EUV maskblanks, substrates with a multilayer reflective film and substrates.

In addition, in the case of multilayer reflective films of substrateswith a multilayer reflective film used in conventional EUV masks,attempts have been made to reduce concave defects present on thesubstrate by depositing according to, for example, the method describedin Patent Literature 1. However, no matter how much defects attributableto concave defects in the substrate are reduced, due to the highdetection sensitivity of the aforementioned highly sensitive defectdetection apparatuses, there is still the problem of the number ofdefects detected (number of detected defects=number of criticaldefects+number of pseudo defects) being excessively large when themultilayer reflective film is inspected for defects.

Pseudo defects as mentioned here refer to surface irregularities that donot have an effect on pattern transfer and are permitted to be presenton a multilayer reflective film, and end up being incorrectly assessedas defects when inspected with a highly sensitive defect inspectionapparatus. If a large number of such pseudo defects are detected in adefect inspection, critical defects that do affect pattern transfer endup being concealed by the large number of pseudo defects, therebypreventing the discovery of critical defects. For example, withcurrently popular defect inspection apparatuses employing an inspectionlight source wavelength of 266 nm, 193 nm or 13.5 nm, the number ofdefects detected in a defect inspection region (measuring, for example,132 mm×132 mm) ends up exceeding 50,000 defects in measurement of asubstrate or substrate with a multilayer reflective film having a sizeof, for example, 152 mm×152 mm, thereby obstructing inspections for thepresence of critical defects. Overlooking critical defects in a defectinspection results in defective quality in the subsequent semiconductordevice volume production process and leads to unnecessary labor andeconomic losses.

In view of the foregoing, an object of the present invention is toprovide a substrate with a multilayer reflective film, which is able tofacilitate discovery of contaminants or scratches and other criticaldefects by inhibiting detection of pseudo defects attributable tosurface roughness of a substrate or film in a defect inspection using ahighly sensitive defect inspection apparatus, a reflective mask blank,and a method of manufacturing a semiconductor device.

In addition, an object of the present invention is to provide asubstrate with a multilayer reflective film, which enables criticaldefects to be reliably detected since the number of detected defects,including pseudo defects, is reduced even when using highly sensitivedefect inspection apparatuses that use light of various wavelengths, andachieves smoothness required by substrates having a multilayerreflective film in particular while simultaneously reducing the numberof detected defects, including pseudo defects, a reflective mask blankobtained by using that substrate with a multilayer reflective film, anda semiconductor device that uses that reflective mask blank.

Means for Solving the Problems

As a result of conducting extensive studies to solve the aforementionedproblems, the inventors of the present invention found that theroughness of a prescribed spatial frequency (or spatial wavelength)component affects the inspection light source wavelength of a highlysensitive defect inspection apparatus. Therefore, by specifying thespatial frequency of a roughness component at which a highly sensitivedefect inspection apparatus ends up incorrectly assessing a defect as apseudo defect among roughness (surface irregularity) components on thesurface of a film (such as an absorber film) formed on a main surface ofa substrate, and managing amplitude intensity at that spatial frequency,the detection of pseudo defects in a defect inspection can be inhibitedand critical defects can be made more conspicuous.

In addition, although attempts have previously been made to reduce thesurface roughness of substrates with a multilayer reflective film fromthe viewpoint of reflectance properties, there is no known correlationwhatsoever with the detection of pseudo defects by highly sensitivedefect inspection apparatuses.

Therefore, the present invention has the configurations indicated belowin order to solve the aforementioned problems.

The present invention is a substrate with a multilayer reflective filmcharacterized by the following Configurations 1 to 5, a reflective maskblank characterized by the following Configurations 6 to 8, a reflectivemask characterized by the following Configuration 9, and a method ofmanufacturing a semiconductor device characterized by the followingConfiguration 10.

(Configuration 1)

Configuration 1 of the present invention is a substrate with amultilayer reflective film, comprising: a multilayer reflective filmobtained by alternately laminating a high refractive index layer and alow refractive index layer on or above a main surface of a mask blanksubstrate used in lithography; wherein, an integrated value I of thepower spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹of the surface of the substrate with a multilayer reflective film,obtained by measuring a region measuring 3 μm×3 μm with an atomic forcemicroscope, is not more than 180×10⁻³ nm³, and the maximum value of thepower spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹is not more than 50 nm⁴.

According to Configuration 1, by making the integrated value I of thepower spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10μm⁻¹, obtained by measuring a region measuring 3 μm×3 μm on the surfaceof a reflective mask blank, to be not more than 180×10⁻³ nm³, and makingthe maximum value of the power spectrum density (PSD) at a spatialfrequency of 1 μm⁻¹ to 10 μm⁻¹ to be not more than 50 nm⁴, detection ofpseudo defects in a defect inspection, using a highly sensitive defectinspection apparatus having an inspection wavelength of the defectinspection light source of 150 nm to 365 nm, can be inhibited whilemaking critical defects more conspicuous. Moreover, detection of pseudodefects under a plurality of levels of inspection sensitivityconditions, using a highly sensitive defect inspection apparatus havingan inspection wavelength of the defect inspection light source of 150 nmto 365, can also be inhibited while making critical defects moreconspicuous.

(Configuration 2)

Configuration 2 of the present invention is the substrate with amultilayer reflective film as described in Configuration 1, wherein theintegrated value I of the power spectrum density (PSD) at a spatialfrequency of 1 μm⁻¹ to 5 μm⁻¹ of the surface of the substrate with amultilayer reflective film, obtained by measuring a region measuring 3μm×3 μm with an atomic force microscope, is not more than 115×10⁻³ nm³.

According to Configuration 2, detection of pseudo defects in a defectinspection, using a highly sensitive defect inspection apparatus havingan inspection wavelength of the defect inspection light source of 150 nmto 365 nm, can be inhibited while making critical defects moreconspicuous.

(Configuration 3)

Configuration 3 of the present invention is the substrate with amultilayer reflective film as described in Configuration 1 orConfiguration wherein the power spectrum density at a spatial frequencyof 1 μm⁻¹ to 10 μm⁻¹ has the characteristic of an overall monotonicdecrease.

As shown in FIG. 7, for example, “overall monotonic decrease” refers toa gradual decrease in power spectrum density such that an approximationcurve approaches a high spatial frequency of 10 μm⁻¹ from a low spatialfrequency of 1 μm⁻¹ when the relationship between spatial frequency andpower spectrum density is approximated by a prescribed approximationcurve. In the example shown in FIG. 7, a power approximation is used forthe approximation curve.

According to Configuration 3, as a result of power spectrum density overa prescribed spatial frequency range having the characteristic of anoverall monotonic decrease, detection of pseudo defects in a defectinspection using a highly sensitive defect inspection apparatus can befurther inhibited while making critical defects even more conspicuous.

(Configuration 4)

Configuration 4 of the present invention is a substrate with amultilayer reflective film, comprising: a multilayer reflective filmobtained by alternately laminating a high refractive index layer and alow refractive index layer on or above a main surface of a mask blanksubstrate used in lithography; wherein, an integrated value I of thepower spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to 100μm⁻¹ of the surface of the substrate with a multilayer reflective film,obtained by measuring a region measuring 1 μm×1 μm with an atomic forcemicroscope, is not more than 150×10⁻³ nm³, and the maximum value of thepower spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to 100μm⁻¹ is not more than 9 nm⁴.

According to Configuration 4, by making the integrated value I of thepower spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to 100μm⁻¹, obtained by measuring a region measuring 1 μm×1 μm on the surfaceof a reflective mask blank, to be not more than 150×10⁻³ nm³, and makingthe maximum value of the power spectrum density (PSD) at a spatialfrequency of 10 μm⁻¹ to 100 μm⁻¹ to be not more than 9 nm⁴, thedetection of pseudo defects in a detect inspection using a highlysensitive defect inspection apparatus having an inspection wavelength ofthe defect inspection light source of 0.2 nm to 100 nm can be inhibitedwhile making critical defects more conspicuous. Moreover, detection ofpseudo defects under a plurality of levels of inspection sensitivityconditions using a highly sensitive defect inspection apparatus havingan inspection wavelength of the defect inspection light source of 0.2 nmto 100 nm can also be inhibited while making critical defects moreconspicuous.

(Configuration 5)

Configuration 5 of the present invention is the substrate with amultilayer reflective film as described in Configuration 4, wherein thepower spectrum density at a spatial frequency of 10 μm⁻¹ to 100 μm⁻¹ hasthe characteristic of an overall monotonic decrease.

Furthermore, the overall monotonic decrease referred to here has thesame meaning as previously described, and as shown in FIG. 8, forexample, refers to a gradual decrease in power spectrum density suchthat an approximation curve approaches a high spatial frequency of 100μm⁻¹ from a low spatial frequency of 10 μm⁻¹ when the relationshipbetween spatial frequency and power spectrum density is approximated bya prescribed approximation curve. In the example shown in FIG. 8, apower approximation is used for the approximation curve.

According to Configuration 5, the detection of pseudo defects in adefect inspection using a highly sensitive defect inspection apparatuscan be further inhibited while making critical defects even moreconspicuous.

(Configuration 6)

Configuration 6 of the present invention is the substrate with amultilayer reflective film as described in any of Configuration 1 to 5,wherein a protective film is provided on or above the multilayerreflective film.

According to Configuration 6, because damage to the surface of themultilayer reflective film can be inhibited when fabricating a transfermask (EUV mask) as a result of the substrate with a multilayerreflective film having a protective film on or above the multilayerreflective film, reflectance properties with respect to EUV light can befurther improved. In addition, in a substrate with a multilayerreflective film, detection of pseudo defects in a defect inspection ofthe surface of the protective film using a highly sensitive defectinspection apparatus can be inhibited and critical defects can be madeto be more conspicuous.

(Configuration 7)

Configuration 7 of the present invention is a reflective mask blankcomprising an absorber film serving as a transfer pattern on or abovethe multilayer reflective film or the protective film of the substratewith a multilayer reflective film as described in any of Configurations1 to 6.

As a result of having an absorber film serving as a transfer pattern onor above the multilayer reflective film or the protective film of thesubstrate with a multilayer reflective film, a reflective mask blank canbe obtained in which detection of pseudo defects in a defect inspectionusing a highly sensitive defect inspection apparatus can be inhibitedand critical defects can be made to be more conspicuous.

(Configuration 8)

Configuration 8 of the present invention is a reflective mask blankcomprising: a multilayer reflective film, obtained by alternatelylaminating a high refractive index layer and a low refractive indexlayer on or above a main surface of a mask blank substrate used inlithography, and an absorber film; wherein, an integrated value I of thepower spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹of the surface of the absorber film, obtained by measuring a regionmeasuring 3 μm×3 μm with an atomic force microscope, is not more than800×10⁻³ nm³, and the maximum value of the power spectrum density (PSD)at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ is not more than 50 nm⁴.

According to the reflective mask blank of Configuration 8, a reflectivemask blank can be obtained in which detection of pseudo defects in adefect inspection using a highly sensitive defect inspection apparatuscan be inhibited and critical defects can be made to be moreconspicuous.

(Configuration 9)

Configuration 9 of the present invention is a reflective maskcomprising: an absorber pattern on or above the multilayer reflectivefilm or the protective film by patterning the absorber film in thereflective mask blank as described in Configuration 7 or Configuration8.

According to the reflective mask of Configuration 9, detection of pseudodefects in a defect inspection using a highly sensitive defectinspection apparatus can be inhibited and critical defects can be madeto be more conspicuous.

(Configuration 10)

Configuration 10 of the present invention is a method of manufacturing asemiconductor device comprising a step for forming a transfer pattern onor above a transferred substrate by carrying out a lithography processwith an exposure apparatus using the reflective mask as described inConfiguration 9.

According to the method of manufacturing a semiconductor device ofConfiguration 10, because a reflective mask from which contaminants,scratches and other critical defects have been removed can be used in adefect inspection using a highly sensitive defect inspection apparatus,a circuit pattern or other transfer pattern transferred to a resist filmformed on or above a transferred substrate such as a semiconductorsubstrate is free of defects, and a semiconductor device can befabricated that has a fine and highly precise transfer pattern.

Effects of the Invention

According to the substrate with a multilayer reflective film, reflectivemask blank and reflective mask of the present invention as previouslydescribed, the discovery of contaminants, scratches or other criticaldefects can be facilitated by inhibiting detection of pseudo defectsattributable to surface roughness of a substrate or film in a defectinspection using a highly sensitive defect inspection apparatus. In asubstrate with a multilayer reflective film, reflective mask blank andreflective mask used in EUV lithography in particular, a multilayerreflective film formed on a main surface of a substrate is obtained thatexhibits high reflectance while inhibiting pseudo defects.

In addition, according to the method of manufacturing a semiconductordevice as previously described, because a reflective mask from whichcontaminants, scratches and other critical defects have been removed canbe used in a defect inspection using a highly sensitive defectinspection apparatus, a circuit pattern or other transfer pattern formedon a transferred substrate such as a semiconductor substrate is free ofdefects, and a semiconductor device can be fabricated that has a fineand highly precise transfer pattern.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1(a) is a perspective view showing a mask blank substrate accordingto one embodiment of the present invention. FIG. 1(b) is across-sectional schematic diagram showing a mask blank substrate of theembodiment.

FIG. 2 is a cross-sectional schematic diagram showing one example of theconfiguration of a substrate with a multilayer reflective film accordingto one embodiment of the present invention.

FIG. 3 is a cross-sectional schematic diagram showing one example of theconfiguration of a reflective mask blank according to one embodiment ofthe present invention.

FIG. 4 is a cross-sectional schematic diagram showing one example of areflective mask according to one embodiment of the present invention.

FIG. 5 is a graph indicating the results of analyzing the power spectraof the surfaces of substrates with a multilayer reflective film of anExample 1 and Comparative Example 1 of the present invention, andindicates the power spectrum densities (PSD) at spatial frequenciesobtained by measuring a region measuring 1 μm×1 μm with an atomic forcemicroscope.

FIG. 6 is a graph indicating the results of analyzing the power spectraof the surfaces of substrates with a multilayer reflective film of anExample 1 and Comparative Example 1 of the present invention, andindicates the power spectrum densities (PSD) at spatial frequenciesobtained by measuring a region measuring 3 μm×3 μm with an atomic forcemicroscope.

FIG. 7 indicates the results of subjecting the data shown in FIG. 6 topower approximation over a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹.

FIG. 8 indicates the results of subjecting the data shown in FIG. 5 topower approximation over a spatial frequency of 10 μm⁻¹ to 100 μm⁻¹.

FIG. 9 is a schematic diagram of a catalyst-referred etching (CARE)apparatus used in an example.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is a substrate with a multilayer reflective filmhaving a mask blank multilayer film obtained by alternately laminating ahigh refractive index layer and a low refractive index layer on or abovea main surface of a mask blank substrate used in lithography. Inaddition, the present invention is a reflective mask blank comprising amultilayer reflective film, obtained by alternately laminating a highrefractive index layer and a low refractive index layer on or above amain surface of a mask blank substrate used in lithography, and anabsorber film. The substrate with a multilayer reflective film andreflective mask blank of the present invention can be used to fabricatea reflective mask used in EUV lithography.

FIG. 2 is a schematic diagram of one example of a substrate with amultilayer reflective film 20 of the present invention. The substratewith a multilayer reflective film 20 of the present invention has amultilayer reflective film 21 on or above a main surface of a mask blanksubstrate 10. The substrate with a multilayer reflective film 20 of thepresent invention may further comprise a protective film 22 on or abovethe multilayer reflective film 21. A reflective mask blank 30 shown inFIG. 3 can be obtained by further forming an absorber film 24 on orabove the substrate with a multilayer reflective film 20 of the presentinvention. A reflective mask 40 shown in FIG. 4 can be fabricated byforming an absorber pattern 27 by patterning the absorber film 24 of thereflective mask blank 30 shown in FIG. 3.

The surfaces of the substrate with a multilayer reflective film 20 andthe reflective mask blank 30 of the present invention are characterizedin that an integrated value I and maximum value of the power spectrumdensity (PSD) over a prescribed spatial frequency range, obtained bymeasuring a region of a prescribed size with an atomic force microscope,fall within a prescribed range. In the substrate with a multilayerreflective film 20 and the reflective mask blank 30 of the presentinvention, the discovery of contaminants, scratches and other criticaldefects can be facilitated by inhibiting the detection of pseudo defectsattributable to the surface roughness of a substrate and film in adefect inspection using a highly sensitive defect inspection apparatus.

[Power Spectrum Analysis]

In the present invention, in order to achieve the aforementioned object,the surface of the substrate with a multilayer reflective film 20 and/orthe reflective mask blank 30 is characterized by having a certainsurface roughness and power spectrum density (PSD).

The following provides an explanation of parameters indicating thesurface morphology of the surfaces of the substrate with a multilayerreflective film 20 and the reflective mask blank 30 of the presentinvention in the form surface roughness (Rmax, RMS) and power spectrumdensity (PSD).

First, RMS (root mean square), which is a typical indicator of surfaceroughness, refers to root mean square roughness and is the square rootof the value obtained by averaging the squares of the deviation from anaverage line to a measurement curve, RMS is represented by the followingformula (1):

$\begin{matrix}\left\lbrack {{Equation}\mspace{14mu} 1} \right\rbrack & \; \\{{Rms} = \sqrt{\frac{1}{l}{\int_{0}^{1}{{Z^{2}(x)}\ d\; x}}}} & (1)\end{matrix}$wherein, l represents a reference length and Z represents the heightfrom the average line to the measurement curve.

Similarly, Rmax, which is also a typical indicator of surface roughness,is the maximum height of surface roughness, and is the differencebetween the absolute values of the maximum value of peak height and themaximum value of trough depth on a roughness curve.

RMS and Rmax have conventionally been used to manage the surfaceroughness of the mask blank substrate 10, and are superior with respectto enabling surface roughness to be ascertained in terms of numericalvalues. However, because RMS and Rmax both only consist of informationrelating to height, they do not provide information relating to subtlechanges in surface morphology.

In contrast, power spectrum analysis, which represents surface roughnesswith an amplitude intensity at a spatial frequency by converting surfaceirregularities of the resulting surface to spatial frequency regions,enables quantification of subtle changes in surface morphology. WhenZ(x,y) is taken to represent height data at an x coordinate and ycoordinate, then the Fourier transformation thereof is given by thefollowing equation (2).

$\begin{matrix}\left\lbrack {{Equation}\mspace{14mu} 2} \right\rbrack & \; \\{{F\left( {u,v} \right)} = {\frac{1}{N_{x}N_{y}}{\sum\limits_{u = 0}^{N_{x} - 1}{\sum\limits_{v = 0}^{N_{y} - 1}{{Z\left( {x,y} \right)}{\exp\left\lbrack {{- i}\; 2{\pi\left( {\frac{u\; x}{N_{x}} + \frac{v\; y}{N_{y}}} \right)}} \right\rbrack}}}}}} & (2)\end{matrix}$

Here, N_(x) and N_(y) represent the number of data sets in the xdirection and y direction. u represents 0, 1, 2, . . . Nx−1, vrepresents 0, 1, 2 . . . Ny−1, and spatial frequency f at this time isgiven by the following equation (3).

$\begin{matrix}\left\lbrack {{Equation}\mspace{14mu} 3} \right\rbrack & \; \\{f = \left\{ {\left\lbrack \frac{u}{\left( {N_{x} - 1} \right)d_{x}} \right\rbrack^{2} + \left\lbrack \frac{v}{\left( {N_{y} - 1} \right)d_{y}} \right\rbrack^{2}} \right\}^{1/2}} & (3)\end{matrix}$

Here, in equation (3), d_(x) represents the minimum resolution in the xdirection while d_(y) represents the minimum resolution in the ydirection.

Power spectrum density PSD at this time is given by the followingequation (4).

[Equation 4]P(u,v)=|F(u,v)|²  (4)

This power spectrum analysis is superior in that it not only makes itpossible to ascertain changes in the surface morphology of a mainsurface 2 of the substrate 10, the substrate with a multilayerreflective film 20 and a film such as the reflective mask blank 30 assimple changes in height, but also as changes at that spatial frequency,and enables analysis of the effects of microscopic reactions and thelike on the surface at the atomic level.

An integrated value I of power spectrum density (PSD) can be used in thecase of evaluating the surface morphology of the substrate with amultilayer reflective film 20 and the reflective mask blank 30 by powerspectrum analysis. The integrated value I refers to an area over therange of a prescribed spatial frequency depicted by the value of powerspectrum density (PSD) relative to spatial frequency as exemplified inFIG. 5, and is defined as shown in equation (5).

$\begin{matrix}\left\lbrack {{Equation}\mspace{14mu} 5} \right\rbrack & \; \\{I = {\sum\limits_{i}{\left( {f_{i + 1} - f_{i}} \right){P\left( f_{i} \right)}}}} & (5) \\\left\lbrack {{Equation}\mspace{14mu} 6} \right\rbrack & \; \\{{f_{i} = \frac{i}{X^{\prime}}},{i = 1},2,{\cdots\mspace{14mu}\frac{N^{\prime}}{2}}} & (6)\end{matrix}$

Spatial frequency f is defined in the manner of equation (3), and powerspectrum density is fundamentally calculated as a function of spatialfrequency determined by the values of u and v. Here, in order tocalculate power spectrum density for a discrete spatial frequency,spatial frequency f_(i) is defined in the manner of equation (6) whenthe measured region and number of data points are equal in the xdirection and y direction. Here, X′ and N′ represent the measured regionand number of data points. P(f_(i)) is the power spectrum density atspatial frequency f_(i).

In the present invention, when measuring a region of a prescribed size,such as a region measuring 3 μm×3 μm, in order to analyze a powerspectrum, the measured region may be any arbitrary location of a regionwhere a transfer pattern is formed. In the case the size of the maskblank substrate 10 is that of a 6025 plate (152 mm×152 mm×6.35 mm), thenthe transfer pattern formation region can be, for example, a regionmeasuring 142 mm×142 trim, a region measuring 132 mm×132 mm or a regionmeasuring 132 mm×104 mm obtained by excluding the peripheral region ofthe surface of the reflective mask blank 30. In addition, theaforementioned arbitrary location may be a region located in the centerof the surface of the reflective mask blank 30, for example.

In addition, the previously described 3 μm×3 μm region, the transferpattern formation region, and the arbitrary location may also be appliedto the mask blank substrate 10 and the absorber film 24 of thereflective mask blank 30.

As a result of making the surface roughness and power spectrum densityof a main surface fall within the ranges described above, the detectionof pseudo defects can be significantly inhibited in a defect inspectionby for example, the “MAGICS M7360” Mask/Substrate/Blank DefectInspection Apparatus for EUV Exposure manufactured by Lasertee Corp.(inspection light source wavelength: 266 nm), or the “Teron 600 Series”of Reticule, Optical Mask/Blank and UV Mask/Blank Defect InspectionApparatuses manufactured by KLA-Tencor Corp. (such as the “Teron 610”,inspection light source wavelength: 193 nm).

Furthermore, the aforementioned inspection light source wavelength isnot limited to 266 nm and 193 nm. A wavelength of 532 nm, 488 nm, 364 nmand/or 257 nm may also be used as the inspection light sourcewavelength.

When carrying out a defect inspection on a main surface of theaforementioned mask blank substrate 10 using a highly sensitive defectinspection apparatus using inspection light in the wavelength region of0.2 nm to 100 nm (EUV light), such as a highly sensitive defectinspection apparatus using EUV light having an inspection light sourcewavelength of 13.5 nm, the power spectrum density at a spatial frequencyof 10 μm⁻¹ to 100 μm⁻¹ of the aforementioned main surface, obtained bymeasuring a 1 μm×1 μm region with an atomic force microscope, ispreferably not more than 5 nm⁴, and the power spectrum density at aspatial frequency of 10 μm⁻¹ to 100 μm⁻¹ is more preferably 0.5 nm⁴ to 5nm⁴. However, when carrying out a defect inspection on a main surface ofthe mask blank substrate 10 using a highly sensitive defect inspectionapparatus using HIV light, this is limited to the case of a materialother than glass, because a minimum prescribed reflectance is required.

As a result of making the surface roughness and power spectrum densityof a main surface fall within the ranges described above, the detectionof pseudo defects can be significantly inhibited in a defect inspectionby, for example, a highly sensitive defect inspection apparatus usingEUV light having a wavelength of 13.5 nm for the inspection light sourcewavelength.

[Mask Blank Substrate 10]

Next, an explanation is provided of the mask blank substrate 10 used inone embodiment of the present invention.

FIG. 1(a) is a perspective view showing the mask blank substrate 10 ofthe present embodiment. FIG. 1(b) is a cross-sectional schematic diagramof the mask blank substrate 10 of the present embodiment.

The mask blank substrate 10 (which may be simply referred to as thesubstrate 10) is a rectangular plate-like body, and has two opposingmain surfaces 2 and an edge face 1. The two opposing main surfaces 2constitute an upper surface and a lower surface of this plate-like body,and are formed so as to be mutually opposed. In addition, at least oneof the two opposing main surfaces 2 is a main surface on which atransfer pattern is to be formed.

The edge face 1 constitutes the lateral surface of this plate-like body,and is adjacent to the outer edges of the opposing main surfaces 2. Theedge face 1 has a flat edge face portion 1 d and a curved edge faceportion 1 f. The flat edge face portion 1 d is a surface that connects aside of one of the opposing main surfaces 2 and a side of the otheropposing main surface 2, and comprises a lateral surface portion 1 a anda chamfered surface portion 1 b. The lateral surface portion 1 a is aportion (T surface) that is nearly perpendicular to the opposing mainsurfaces 2 in the flat edge face portion 1 d. The chamfered surfaceportion 1 b is a portion (C surface) that is chamfered between thelateral surface portion 1 a and the opposing main surfaces 2, and isformed between the lateral surface portion 1 a and the opposing mainsurfaces 2

The curved edge face portion 1 f is a portion (R portion) that isadjacent to the vicinity of a corner portion 10 a of the substrate 10when the substrate 10 is viewed from overhead, and comprises a lateralsurface portion 1 c and a chamfered surface portion 1 e. Here, viewingthe substrate 10 from overhead means that the substrate 10 is visiblefrom, for example, a direction perpendicular to the opposing mainsurfaces 2. In addition, the corner portion 10 a of the substrate 10refers to, for example, the vicinity of the intersection of two sidesalong the outer edge of the opposing main surfaces 2. An intersection oftwo sides refers to the intersection of lines respectively extendingfrom two sides. In the present example, the curved end face portion 1 fis formed into a curved shape by rounding the corner portion 10 a of thesubstrate 10.

In order to achieve the aforementioned object, the main surface of themask blank substrate 10 of the present embodiment where a transferpattern is formed has a root mean square roughness (RMS) of not morethan 0.15 nm, and a power spectrum density at a spatial frequency of notless than 1 μm⁻¹ of not more than 10 nm⁴, as obtained by measuring a 1μm×1 μm region with an atomic force microscope using the aforementionedsurface roughness (RMS) and power spectrum density.

In the present invention, the aforementioned 1 μm×1 μm region may be anyarbitrary location in a transfer pattern formation region. When the sizeof the substrate 10 is that of a 6025 plate (152 mm×152 mm×6.35 mm), thetransfer pattern formation region can be, for example, a regionmeasuring 142 mm×142 mm, a region measuring 132 mm×132 mm or a regionmeasuring 132 mm×104 mm obtained by excluding the peripheral region ofthe main surface of the substrate 10, and the aforementioned arbitrarylocation can be, for example, a region located in the center of the mainsurface of the substrate 10.

In addition, when carrying out a defect inspection on a main surface ofthe aforementioned mask blank substrate 10 using a highly sensitivedefect inspection apparatus using a UV laser having a wavelength of 266nm or an ArF excimer laser having a wavelength of 193 nm for thewavelength of the inspection light source, the power spectrum density ata spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ obtained by measuring a 3 μm×3μm region of the aforementioned main surface with an atomic forcemicroscope is preferably not more than 30 nm⁴, the power spectrumdensity at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ is more preferably 1nm⁴ to 25 nm⁴, and the power spectrum density at a spatial frequency of1 μm⁻¹ to 10 μm⁻¹ is even more preferably 1 nm⁴ to 20 nm⁴.

Moreover, the integrated value I of power spectrum density (PSD) at aspatial frequency of 1 μm⁻¹ to 10 μm⁻¹ obtained by measuring a 3 μm×3 μmregion on a main surface of the mask blank substrate 10 with an atomicforce microscope is preferably not more than 100×10⁻³ nm³, morepreferably not more than 90×10⁻³ nm³, even more preferably not more than80×10⁻³ nm³, and still more preferably not more than 70×10⁻³ nm³.

In addition, the aforementioned root mean square roughness (RMS) ispreferably not more than 0.12 nm, more preferably not more than 0.10 nm,even more preferably not more than 0.08 nm and still more preferably notmore than 0.06 nm. In addition, the maximum height of surface roughness(Rmax) is preferably not more than 1.2 nm, more preferably not more than1.0 nm, even more preferably not more than 0.8 nm, and still morepreferably not more than 0.6 nm. It is preferable to manage both theparameters of root mean square roughness (RMS) and maximum height (Rmax)of the multilayer reflective film 21, the protective film 22 and theabsorber film 24 formed on the mask blank substrate 10 from theviewpoint of improving reflectance and other optical properties. Forexample, the surface roughness of the surface of the mask blanksubstrate 10 is preferably such that the root mean square roughness(RMS) is not more than 0.12 nm and the maximum height (Rmax) is not morethan 1.2 nm, more preferably such that the root mean square roughness(RMS) is not more than 0.10 nm and the maximum height (Rmax) is not morethan 1.0 nm, even more preferably such that the root mean squareroughness (RMS) is not more than 0.08 nm and the maximum height (Rmax)is not more than 0.8 ma, and still more preferably such that the rootmean square roughness (RMS) is not more than 0.06 nm and the maximumheight (Rmax) is not more than 0.6 nm.

A main surface of the mask blank substrate 10 is preferably processed bycatalyst-referred etching. Catalyst-referred etching (to also bereferred to as CARE) refers to a surface processing method involvingarranging a processing target (mask blank substrate) and catalyst in atreatment liquid or supplying a treatment liquid between the processingtarget and the catalyst, allowing the processing target and catalyst tomake contact, and processing the processing target with an activespecies generated from molecules in the treatment liquid that have beenadsorbed onto the catalyst at that time. Furthermore, in the case theprocessing target is composed of a solid oxide such as glass, water isused for the treatment liquid, the processing target and the catalystare allowed to make contact in the presence of the water, and thecatalyst and surface of the processing target are allowed to undergorelative motion and the like to remove decomposition products ofhydrolysis from the surface of the processing target.

A typical CARE processing apparatus is shown in FIG. 9. This CAREprocessing apparatus 100 has a treatment tank 124, a catalyst surfaceplate 126 rotatably arranged in the treatment tank 124, and a substrateholder 130 that removably holds a glass substrate (processing target)128 with the surface (processed surface) facing downward. The substrateholder 130 is coupled to the end of a vertically movable rotating shaft132 provided at a position in parallel with and offset from the centerof the axis of rotation of the catalyst surface plate 126. The catalystsurface plate 126 consists of platinum 142, for example, having aprescribed thickness for use as a solid catalyst formed on the surfaceof a base 140 made of a rigid material composed of stainless steel, forexample. Furthermore, although a bulk material may be used for the solidcatalyst, it may also employ a configuration in which the platinum 142is formed on an elastic base material such as fluorine-based rubber thatis inexpensive and has favorable shape stability. In addition, withinthe substrate holder 130, a temperature control mechanism in the form ofa heater 170 is embedded extending into the rotating shaft 132 in orderto control the temperature of the glass substrate 128 held with theholder 130. A treatment liquid supply nozzle 174 is arranged above thetreatment tank 124 that supplies treatment liquid (water), controlled toa prescribed temperature by a temperature control mechanism in the formof heat exchanger 172, to the treatment tank 124. Moreover, atemperature control mechanism in the form of a fluid flow path 176 isprovided within the catalyst surface plate 126 that controls thetemperature of the catalyst surface plate 126.

Etching by CARE using this CARE processing apparatus 100 is carried outin the manner indicated below. Treatment liquid is supplied from thetreatment liquid supply nozzle 174 towards the catalyst surface plate126. The processing target 128 held with the substrate holder 130 isthen pressed onto the surface of the platinum (catalyst) 142 of thecatalyst surface plate 126 at a prescribed pressure, and the catalystsurface plate 126 and the processing target 128 are rotated whileintroducing treatment liquid into the area where the processing target128 and the platinum (catalyst) 142 of the catalyst surface plate 126make contact (contact portion) to remove and flatten the surface (lowersurface) of the processing target 128. Furthermore, the surface of theprocessing target 128 may also be removed and flattened (etched) bybringing the processing target 128 into extremely close proximity to theplatinum (catalyst) 142 without pressing the processing target 128 heldwith the substrate holder 30 onto the platinum (catalyst) 142 of thecatalyst surface plate 126 at a prescribed pressure.

Because the main surfaces of the mask blank substrate 10 are selectivelyprocessed by catalyst-referred etching starting from protrusions thatcontact a reference surface in the form of a catalyst surface, surfaceirregularities (surface roughness) that compose the main surfaces retainan extremely high level of smoothness while having an extremely uniformsurface morphology, thereby resulting in a surface morphology in whichthe proportion of concave portions is greater than the proportion ofconvex portions with respect to the reference surface. Thus, whenlaminating a plurality of thin films on the aforementioned mainsurfaces, the size of defects on the main surfaces tends to becomesmall, thereby making this preferable in terms of improving defectquality. This effect is especially demonstrated when forming themultilayer reflective film 21 to be subsequently described on anaforementioned main surface in particular. In addition, as a result oftreating a main surface by catalyst-referred etching as previouslydescribed, a surface having the required surface roughness and powerspectrum density can be formed comparatively easily.

Furthermore, in the case the material of the substrate 10 is a glassmaterial, at least one type of material selected from the groupconsisting of platinum, gold, transition metals and alloys comprising atleast one of these materials can be used for the catalyst. In addition,at least one type of treatment liquid selected from the group consistingof pure water, functional water such as ozonated water or hydrogenwater, low-concentration aqueous alkaline solutions andlow-concentration aqueous acidic solutions can be used for the treatmentliquid.

A main surface on the side of the mask blank substrate 10 of the presentembodiment on which a transfer pattern is formed is preferably processedso as to have high flatness at least from the viewpoints of obtainingpattern transfer accuracy and positional accuracy. In the case of an EUVreflective mask blank substrate 10, flatness in a region measuring 132mm×132 mm or a region measuring 142 mm×142 mm on a main surface of thesubstrate 10 on the side on which a transfer pattern is formed ispreferably not more than 0.1 μm and particularly preferably not morethan 0.05 μm. In addition, flatness in a region measuring 132 mm×132 mmon a main surface of the substrate 10 on which a transfer pattern isformed is more preferably not more than 0.03 μm. In addition, the mainsurface on the opposite side from the side on which a transfer patternis formed is the side that is clamped with an electrostatic chuck whenthe substrate is placed in an exposure apparatus, and flatness in aregion measuring 142 mm×142 mm is preferably not more than 1 μm andparticularly preferably not more than 0.5 μm.

Any material may be used for the material of the reflective mask blanksubstrate 10 for EUV exposure provided it has low thermal expansionproperties. For example, a SiO₂—TiO₂-based glass having low thermalexpansion properties (such as a two-element system (SiO₂—TiO₂) orthree-element system (such as SiO₂—TiO₂—SnO₂)), or a so-calledmulticomponent glass such as SiO₂—Al₂O₃—Li_(z)O-based crystallizedglass, can be used. In addition, a substrate other than theaforementioned glass made of silicon or metal and the like can also beused. An example of the aforementioned metal substrate is an invar alloy(Fe—Ni-based alloy).

As was previously described, in the case of the mask blank substrate 10for EUV exposure, although a multicomponent glass material is used sincethe substrate is required to have low thermal expansion properties,there is the problem of it being difficult to obtain high smoothness incomparison with synthetic quartz glass. In order to solve this problem,a thin film composed of a metal or an alloy, or a thin film composed ofa material containing at least one of oxygen, nitrogen and carbon in ametal or alloy, is formed on a substrate composed of a multicomponentglass material. A surface having a surface roughness and a powerspectrum density within the specified ranges can then be formedcomparatively easily by subjecting the surface of this thin film tomirror polishing and surface treatment.

Preferable examples of the material of the aforementioned thin filminclude Ta (tantalum), alloys containing Ta, and Ta compounds containingat least one of oxygen, nitrogen and carbon therein. Examples of Tacompounds that can be used include those selected from TaB, TaN, TaO,TaON, TaCON, TaBN, TaBO, TaBON, TaBCON, TaHf, TaHfO, TaHfN, TaHfON,TaHfCON, TaSi, TaSiO, TaSiN, TaSiON and TaSiCON. Among these Tacompounds, those selected from TaN, TaON, TaCON, TaBN, TaBON, TaBCON,TaHfN, TaHfON, TaHfCON, TaSiN, TaSiON and TaSiCON that contain nitrogen(N) are used more preferably. Furthermore, from the viewpoint of highsmoothness of the thin film surface, the aforementioned thin filmpreferably has a microcrystalline structure or amorphous structure. Thecrystal structure of the thin film can be measured with an X-raydiffraction (XRD) analyzer.

Furthermore, in the present invention, there are no particularlimitations on the processing method used to obtain the previouslydefined surface roughness and power spectrum density. The presentinvention is characterized by managing the surface roughness and powerspectrum density of the mask blank substrate 10, and can be realized by,for example, processing methods like those exemplified in the examplesto be subsequently described.

[Substrate with Multilayer Reflective Film 20]

The following provides an explanation of the substrate with a multilayerreflective film 20 according to one embodiment of the present invention.

FIG. 2 is a schematic diagram showing the substrate with a multilayerreflective film 20 of the present embodiment.

The substrate with a multilayer reflective film 20 of the presentembodiment has a structure having the multilayer reflective film 21 onor above a main surface of the previously explained mask blank substrate10 on the side on which a transfer pattern is formed. This multilayerreflective film 21 imparts a function of reflecting EUV light in areflective mask 40 for EUV lithography, and adopts a configuration inwhich elements having different refractive indices are cyclicallylaminated.

Although there are no particular limitations on the material of themultilayer reflective film 21 provided it reflects EUV light, thereflectance of the multilayer reflective film 21 alone is normally notless than 65% and the upper limit thereof is normally 73%. This type ofmultilayer reflective film 21 can be that of a multilayer reflectivefilm 21 in which a thin film composed of a high refractive indexmaterial (high refractive index layer) and a thin film composed of a lowrefractive index material (low refractive index layer) are alternatelylaminated for about 40 to 60 cycles.

For example, the multilayer reflective film 21 for EUV light of awavelength of 13 nm to 14 nm preferably consists of an Mo/Si cyclicallylaminated film obtained by alternately laminating about 40 cycles of anMo film and Si film. In addition, a multilayer reflective film 21 usedin the region of FIN light can consist of, for example, an Ru/Sicyclically laminated film, Mo/Be cyclically laminated film, Mocompound/Si compound cyclically laminated film, Si/Nb cyclicallylaminated film, Si/Mo/Ru cyclically laminated film, Si/Mo/Ru/Mocyclically laminated film or Si/Ru/Mo/Ru cyclically laminated film.

Although the method used to form the multilayer reflective film 21 isknown in the art, the multilayer reflective film 21 can be formed bydepositing each layer by, for example, magnetron sputtering or ion beamsputtering. In the case of the aforementioned Mo/Si cyclically laminatedfilm, an Si film having a thickness of about several is first depositedon the substrate 10 using an Si target by, for example, ion beamsputtering, followed by depositing an Mo film having a thickness ofabout several nm using an Mo target, with this deposition comprising onecycle, and laminating for 40 to 60 cycles to form the multilayerreflective film 21.

The protective film 22 (see FIG. 3) can be formed to protect themultilayer reflective film 21 from dry etching or wet cleaning in themanufacturing process of the reflective mask 40 for EUV lithography. Inthis manner, an aspect having the multilayer reflective film 21 and theprotective film 22 on the mask blank substrate 10 can also constitutethe substrate with a multilayer reflective film 20 in the presentinvention.

Furthermore, although materials such as Ru, Ru—(Nb, Zr, Y, B, Ti, La,Mo), Si—(Ru, Rh, Cr, B), Si, Zr, Nb, La or B can be used for thematerial of the aforementioned protective film 22, among thesematerials, reflectance properties of the multilayer reflective film 21can be made more favorable if a material comprising ruthenium (Ru) isapplied. More specifically, the material of the protective film 22 ispreferably Ru or Ru—(Nb, Zr, Y, B, Ti, La, Mo). This type of protectivefilm 22 is particularly effective when using a Ta-based material for theabsorber film 24 and patterning the absorber film 24 by dry etching witha Cl-based gas.

The surface of the aforementioned multilayer reflective film 21 or theaforementioned protective film 22 in the substrate with a multilayerreflective film 20 of the present invention has an integrated value I ofpower spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10μm⁻¹, obtained by measuring a 3 μm×3 μm region with an atomic forcemicroscope, of not more than 180×10⁻³ nm³, preferably not more than170×10⁻³ nm³, more preferably not more than 160×10⁻³ nm³ and even morepreferably not more than 150×10⁻³ nm³. Moreover, the surface of theaforementioned multilayer reflective film 21 or the aforementionedprotective film 22 in the aforementioned substrate with a multilayerreflective film 20 has a maximum value of power spectrum density (PSD)at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹, obtained by measuring a 3μm×3 μm region with an atomic force microscope, of not more than 50 nm⁴,preferably not more than 45 nm⁴ and more preferably not more than 40nm⁴. As a result of employing such a configuration, the detection ofpseudo defects in a defect inspection of the surface of the multilayerreflective film 21 or the protective film 22 using a highly sensitivedefect inspection apparatus can be inhibited and critical defects can bemade more conspicuous. In addition, as a result of employing such aconfiguration, when carrying out a defect inspection of the substratewith a multilayer reflective film 20 with a highly sensitive defectinspection apparatus using inspection light of the wavelength region of150 nm to 365 nm, such as the previously exemplified highly sensitivedefect inspection apparatus using a UV laser having a wavelength of 266nm or an ArF excimer laser having a wavelength of 193 nm for thewavelength of the inspection light source, detection of pseudo defectscan be significantly inhibited.

In the present invention, the region of a prescribed size measured withan atomic force microscope in order to analyze power spectrum (theaforementioned 3 μm×3 μm region) may be any arbitrary transfer patternformation region. In the case the size of the substrate 10 is that of a6025 plate (152 mm×152 mm×6.35 mm), the transfer pattern formationregion can be, for example, a region measuring 142 mm×142 mm, a regionmeasuring 132 mm×132 mm or a region measuring 132 mm×104 mm obtained byexcluding the peripheral region of a main surface of the substrate 10,and the aforementioned arbitrary location can be a region located in thecenter of a main surface of the substrate 10, for example.

In the substrate with a multilayer reflective film 20 of the presentinvention, the power spectrum density at a spatial frequency of 1 μm⁻¹to 10 μm⁻¹, obtained by measuring a 3 μm×3 μm region with an atomicforce microscope, has the characteristic of an overall monotonicdecrease.

As shown in FIG. 7, for example, an overall monotonic decrease refers toa gradual decrease in power spectrum density such that an approximationcurve approaches a high spatial frequency of 10 μm⁻¹ from a low spatialfrequency of 1 μm⁻¹ when the relationship between spatial frequency andpower spectrum density is approximated by a prescribed approximationcurve. In the example shown in FIG. 7, a power approximation is used forthe approximation curve. In general, data can be approximated by thefollowing power curve equation using power approximation when x isdefined as the spatial frequency and y is defined as power spectrumdensity (PSD).y=a·x ^(b)(wherein, a and b are constants)In the case of power approximation, in the case the exponent value b ofx in the power curve equation is negative, the power spectrum densitycan be said to have the characteristic of an overall monotonic decrease.As a result of power spectrum density within a prescribed spatialfrequency range having the characteristic of an overall monotonicdecrease, detection of pseudo defects in a defect inspection using ahighly sensitive defect inspection apparatus can be further inhibitedwhile making critical defects even more conspicuous.

In the substrate with a multilayer reflective film 20 of the presentinvention, the integrated value I of the power spectrum density (PSD) ata spatial frequency of 1 μm⁻¹ to 5 μm⁻¹ of the surface of theaforementioned multilayer reflective film 21 or the aforementionedprotective film 22, obtained by measuring a 3 μm×3 μm region with anatomic force microscope, is preferably not more than 115×10⁻³ nm³, morepreferably not more than 105×10⁻³ nm³ and even more preferably not morethan 95×10⁻³ nm³. As a result of employing such a configuration, whencarrying out a defect inspection of the substrate with a multilayerreflective film 20 with a highly sensitive defect inspection apparatususing inspection light of the wavelength region of 150 nm to 365 nm,such as the previously exemplified highly sensitive defect inspectionapparatus using a UV laser having a wavelength of 266 nm or an ArFexcimer laser having a wavelength of 193 nm for the wavelength of theinspection light source, detection of pseudo defects can besignificantly inhibited.

In addition, in the substrate with a multilayer reflective film 20 ofthe present invention, the integrated value I of the power spectrumdensity (PSD) at a spatial frequency of 10 μm⁻¹ to 100 μm⁻¹ of thesurface of the aforementioned multilayer reflective film 21 or theaforementioned protective film 22, obtained by measuring a 1 μm×1 μmregion with an atomic force microscope, is not more than 150×10⁻³ nm³,preferably not more than 140×10⁻³ nm³, more preferably not more than135×10⁻³ nm³ and even more preferably not more than 130×10⁻³ nm³.Moreover, in the aforementioned substrate with a multilayer reflectivefilm 20, the maximum value of the power spectrum density (PSD) at aspatial frequency of 10 μm⁻¹ to 100 μm⁻¹ of the surface of theaforementioned multilayer reflective film 21 or the aforementionedprotective film 22 is not more than 9 nm⁴, preferably not more than 8nm⁴, more preferably not more than 7 nm⁴, and even more preferably notmore than 6 nm⁴. As a result of employing such a configuration, whencarrying out a defect inspection of the substrate with a multilayerreflective film 20 with a highly sensitive defect inspection apparatususing inspection light of the wavelength region of 0.2 nm to 100 nm,such as a highly sensitive defect inspection apparatus using EUV lighthaving a wavelength of 13.5 nm for the wavelength of the inspectionlight source, detection of pseudo defects can be significantlyinhibited.

In the substrate with a multilayer reflective film 20 of the presentinvention, power spectrum density at a spatial frequency of 10 μm⁻¹ to100 μm⁻¹, obtained by measuring a 1 μm×1 μm region with an atomic forcemicroscope, preferably has the characteristic of an overall monotonicdecrease. An overall monotonic decrease refers to that previouslyexplained with reference to FIG. 7 with the exception of making thespatial frequency range to be 10 μm⁻¹ to 100 μm⁻¹. As a result of powerspectrum density within a prescribed spatial frequency range having thecharacteristic of an overall monotonic decrease, detection of pseudodefects in a defect inspection using a highly sensitive defectinspection apparatus can be further inhibited and critical defects canbe made to be even more conspicuous.

The substrate with a multilayer reflective film 20 of the presentinvention preferably has the protective film 22 on or above themultilayer reflective film 21. Because damage to the surface of themultilayer reflective film 21 can be inhibited when fabricating atransfer mask (EUV mask) as a result of the substrate with a multilayerreflective film 20 having the protective film 22 on the multiplayerreflective film 21, reflectance properties with respect to EUV light canbe further improved. In addition, in the substrate with a multilayerreflective film 20, detection of pseudo defects in a defect inspectionof the surface of the protective film 22 using a highly sensitive defectinspection apparatus can be inhibited and critical defects can be madeto be more conspicuous. When the substrate with a multilayer reflectivefilm 20 has the protective film 22, the prescribed integrated value I ofpower spectrum density (PSD) and the prescribed maximum value of powerspectrum density (PSD) as previously described can be obtained based ona spatial frequency obtained by measuring the surface of the protectivefilm 22 with an atomic force microscope.

Moreover, in addition to the effect of enabling the detection of pseudodefects to be inhibited significantly in a defect inspection using ahighly sensitive defect inspection apparatus as previously described, inorder to improve reflection properties required for use as the substratewith a multilayer reflective film 20, the root mean square roughness(RMS) of the aforementioned substrate with a multilayer reflective film20 on the surface of the multilayer reflective film 21 or the protectivefilm 22, obtained by measuring a 1 μm×1 μm region with an atomic forcemicroscope, is preferably not more than 0.15 nm. The root mean squareroughness (RMS) is more preferably not more than 0.13 nm and even morepreferably not more than 0.12 nm.

A sputtering method for maintaining the surface morphology of theaforementioned substrate 10 and allowing the surface of the multilayerreflective film 21 or the protective film 22 to have a power spectrumdensity within the aforementioned range is as described below. Namely, asurface having a power spectrum density within the aforementioned rangecan be obtained by depositing the multilayer reflective film 21 bysputtering so that a high refractive index layer and a low refractiveindex layer accumulate on an angle to the normal of a main surface ofthe substrate 10. More specifically, the multilayer reflective film 21is deposited by making the incident angle of sputtered particles fordepositing a low refractive index layer consisting of Mo and the likeand the incident angle of sputtered particles for depositing a highrefractive index layer consisting of Si and the like to be greater than0 degrees to not more than 45 degrees, more preferably greater than 0degrees to not more than 40 degrees, and even more preferably greaterthan 0 degrees to not more than 30 degrees. Moreover, the protectivelayer 22 formed on the multilayer reflective film 21 is also preferablyformed by ion beam sputtering in continuation therefrom so that theprotective layer 22 accumulates on an angle to the normal of a mainsurface of the substrate 10.

In addition, in the substrate with a multilayer reflective film 20, aback side electrically conductive film 23 (see FIG. 3) can also beformed on the surface of the substrate 10 on the opposite side from thesurface contacting the multilayer reflective film 21 for the purpose ofelectrostatic clamping. In this manner, an aspect having the multilayerreflective film 21 and the protective film 22 on the side of the maskblank substrate 10 on which a transfer pattern is formed, and having theback side electrically conductive film 23 on the surface on the oppositeside from the surface contacting the multilayer reflective film 21, alsoconstitutes the substrate with a multi layer reflective film 20 in thepresent invention. Furthermore, the electrical property (sheetresistance) required by the back side electrically conductive film 23 isnormally not more than 100 Ω/square. The method used to form the backside electrically conductive film 23 is a known method. The back sideelectrically conductive film 23 can be formed, for example, using ametal or alloy target of Cr or Ta and the like by magnetron sputteringor ion beam sputtering.

In addition, the substrate with a multilayer reflective film 20 of thepresent embodiment may also have abuse layer formed between thesubstrate 10 and the multilayer reflective film 21. The base layer canbe formed for the purpose of improving smoothness of a main surface ofthe substrate 10, reducing defects, demonstrating the effect ofenhancing reflectance of the multilayer reflective film 21, andcompensating for stress in the multilayer reflective film 21.

[Reflective Mask Blank]

The following provides an explanation of the reflective mask blank 30according to one embodiment of the present invention.

FIG. 3 is a schematic diagram showing the reflective mask blank 30 ofthe present embodiment.

The reflective mask blank 30 of the present embodiment employs aconfiguration in which an absorber film 24 serving as a transfer patternis formed on the protective film 22 of the previously explainedsubstrate with a multilayer reflective film 20.

The aforementioned absorber film 24 is only required to be that whichfunctions to absorb exposure light in the form of EUV light, and has adesired difference in reflectance between light reflected by theaforementioned multilayer reflective film 21 and/or the protective film22 and light reflected by an absorber pattern 27 in a reflective mask 40fabricated using the reflective mask blank 30.

For example, reflectance with respect to EUV light of the absorber film24 is set to between 0.1% and 40%. Moreover, in addition to theaforementioned difference in reflectance, the absorber film 24 may alsohave a desired phase difference between light reflected by theaforementioned multilayer reflective film 21 and/or the protective film22 and light reflected by the absorber pattern 27. Furthermore, in thecase of having such a desired phase difference between reflected light,the absorber film 24 in the reflective mask blank 30 may be referred toas a phase shift film. When the contrast of reflected light of thereflective mask 40 is improved by providing the aforementioned desiredphase difference between reflected light, the phase difference ispreferably set to within the range of 80 degrees±10 degrees, theabsolute reflectance of the absorber film 24 is preferably set to 1.5%to 30%, and the reflectance of the absorber film 24 with respect to thesurface of the multilayer reflective film 21 and/or the protective film22 is preferably set to 2% to 40%.

The aforementioned absorber film 24 may be a single layer or amultilayered structure. In the case of a multilayered structure, thelaminated films may be of the same material or different materials. Thelaminated film can be that in which the materials and/or compositionchange incrementally or continuously in the direction of film thickness.

There are no particular limitations on the material of theaforementioned absorber film 24. For example, a material having thefunction of absorbing EUV light that is composed of Ta (tantalum) aloneor a material having Ta as the main component thereof is usedpreferably. A material having Ta as the main component thereof isnormally a Ta alloy. The crystalline state of this absorber film 24 issuch that it preferably has an amorphous or microcrystalline structurefrom the viewpoints of smoothness and flatness. Examples of materialshaving Ta as the main component thereof include materials containing Taand B, materials containing Ta and N, materials containing Ta and B andfurther containing at least O or N, materials containing Ta and Si,materials containing Ta, Si and N, materials containing Ta and Ge, andmaterials containing Ta, Ge and N. In addition, an amorphous structureis easily obtained by adding, for example, B, Si or Ge and the like toTa, thereby making it possible to improve smoothness. Moreover, if Nand/or O are added to Ta, resistance to oxidation improves, therebymaking it possible to improve stability over time. In order to maintainthe surface morphology of the substrate 10 and the substrate with amultilayer reflective film 20 within the aforementioned ranges and allowthe surface of the absorber film 24 to have a power spectrum densitywithin the aforementioned ranges, a microcrystalline structure oramorphous structure is preferably employed for the absorber film 24.Crystal structure can be confirmed with an X-ray diffraction (XRD)analyzer.

In the reflective mask blank 30 of the present invention, the filmthickness of the absorber film 24 is set to the film thickness requiredfor the absorber film 24 to have the desired difference in reflectancebetween light reflected by the multilayer reflective film 21 and theprotective film 22 and light reflected by the absorber pattern 27. Thefilm thickness of the absorber film 24 is preferably not more than 60 nmin order to reduce shadowing effects.

In addition, in the reflective mask blank 30 of the present invention,the aforementioned absorber film 24 can be given a phase shift functionhaving a desired phase shift difference between light reflected by theaforementioned multilayer reflective film 21 and/or the protective film22 and light reflected by the absorber pattern 27. In that case, theresulting reflective mask blank 30 serves as the master of thereflective mask 40 having improved transfer resolution by EUV light. Inaddition, because the film thickness of the absorber film 24 required todemonstrate a phase shift effect needed to demonstrate desired transferresolution can be reduced in comparison with that in the prior art, areflective mask blank is obtained in which shadowing effects arereduced.

There are no particular limitations on the material of the absorber film24 having a phase shift function. For example, Ta alone or a materialhaving Ta as the main component thereof can be used as previouslydescribed, or another material may be used. Examples of materials otherthan Ta include Ti, Cr, Nb, Mo, Ru, Rh and W. In addition, an alloycontaining two or more elements among Ta, Ti, Cr, Nb, Mo, Ru, Rh and Wcan be used for the material, and/or a multilayer film consisting ofthese elements can be used. In addition, one or more elements selectedfrom nitrogen, oxygen and carbon may also be contained in thesematerials. Among these, by employing a material containing nitrogen, theroot mean square roughness (RMS) and amplitude intensity in the form ofthe power spectrum density of all roughness components at a spatialfrequency of 1 μm⁻¹ to 10 μm⁻¹ detected in a region measuring 3 μm×3 μmof the surface of the absorber film can be reduced, and the reflectivemask blank 30 can be obtained that is able to inhibit the detection ofpseudo defects in a defect inspection using a highly sensitive defectinspection apparatus, thereby making this preferable. Furthermore, inthe case of using the absorber film 24 in the form of a laminated film,the laminated film may be a laminated film consisting of layers of thesame material or a laminated film consisting of layers of differentmaterials. In the case of using a laminated film consisting of layers ofdifferent materials for the absorber film 24, the materials that composethis plurality of layers may be materials having mutually differentetching properties to obtain the absorber film 24 having an etching maskfunction.

The surface of the aforementioned absorber film 24 preferably has apower spectrum density at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹,obtained by a measuring a region measuring 3 μm×3 μm with an atomicforce microscope, of not more than 50 nm⁴, and more preferably has apower spectrum density at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹,obtained by measuring a region measuring 3 μm×3 μm with an atomic forcemicroscope, of not more than 40 nm⁴. As a result of employing such aconfiguration, when carrying out a defect inspection on the reflectivemask blank 30 with a multilayer reflective film 20 with a highlysensitive defect inspection apparatus that uses inspection light in thewavelength region of 150 nm to 365 nm, such as the previously mentionedhighly sensitive inspection apparatus using a ITV laser having aninspection light source wavelength of 266 nm or ArF excimer laser havingan inspection light source wavelength of 193 nm, detection of pseudodefects can be inhibited significantly.

Moreover, in addition to the surface of the aforementioned absorber film24 having a power spectrum density at a spatial frequency of 1 μm⁻¹ to10 μm⁻¹, obtained by a measuring a region measuring 3 μm×3 μm with anatomic force microscope, of not more than 50 nm⁴, the integrated value Iof power spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10μm⁻¹ is preferably not more than 800×10⁻³ nm³. As a result of employingsuch a configuration, detection of pseudo defects under a plurality oflevels of inspection sensitivity conditions using a highly sensitivedefect inspection apparatus that uses inspection light in the wavelengthregion of 150 nm to 365 nm, such as the previously mentioned highlysensitive inspection apparatus using a UV laser having an inspectionlight source wavelength of 266 nm or ArF excimer laser having aninspection light source wavelength of 193 nm, can be inhibited whilemaking critical defects more conspicuous. The aforementioned integratedvalue I is preferably not more than 650×10⁻³ nm³, more preferably notmore than 500×10⁻³ nm³ and particularly preferably not more than450×10⁻³ nm³. The aforementioned integrated value I of the absorber film24 can be adjusted according to such factors as the material,composition, film thickness and deposition conditions of the absorberfilm.

Furthermore, the reflective mask blank 30 of the present invention isnot limited to the configuration shown in FIG. 3. For example, a resistfilm serving as a mask for patterning the aforementioned absorber film24 can also be formed on the absorber film 24, and this reflective maskblank 30 having a resist film can also constitute the reflective maskblank 30 of the present invention. Furthermore, the resist film formedon the absorber film 24 may be a positive resist or negative resist. Inaddition, the resist film may be for electron beam drawing or laserdrawing. Moreover, amu-called hard mask (etching mask) film can also beformed between the absorber film 24 and the aforementioned resist film,and this aspect can also constitute the reflective mask blank 30 of thepresent invention.

A hard mask film 25 may be stripped after having formed a transferpattern on the absorber film 24 or the absorber film 24 may employ alaminated structure consisting of a plurality of layers in thereflective mask blank 30 in which a hard mask film is not formed, andthe materials that compose this plurality of layers may have mutuallydifferent etching properties to obtain a reflective mask blank 30 havingthe absorber film 24 that demonstrates an etching mask function.

[Reflective Mask]

The following provides an explanation of the reflective mask 40according to one embodiment of the present invention.

FIG. 4 is a schematic diagram showing the reflective mask 40 of thepresent embodiment.

The reflective mask. 40 of the present embodiment employs aconfiguration in which the absorber pattern 27 is formed on theaforementioned protective film 22 by patterning the absorber film 24 onthe aforementioned reflective mask blank 30. As a result of exposurelight such as EUV light being absorbed at the portion of the masksurface where the absorber film 24 is present when the reflective mask40 of the present embodiment is exposed with exposure light, andexposure light being reflected by the exposed protective layer 22 andthe multilayer reflective film 21 at other portions where the absorberfilm 24 has been removed, the reflective mask 40 can be used forlithography.

[Method of Manufacturing Semiconductor Device]

A semiconductor device, having various patterns formed on asemiconductor substrate, can be manufactured by transferring a transferpattern, such as a circuit pattern, based on the absorber pattern 27 ofthe reflective mask 40, to a resist film fog wed on a transferredsubstrate such as a semiconductor substrate by using the previouslyexplained reflective mask 40 and a lithography process using an exposureapparatus, followed by going through various other steps.

Furthermore, fiducial marks can be formed on the previously describedmask blank substrate 10, the substrate with a multilayer reflective film20 and the reflective mask blank 30, and the coordinates of thelocations of these fiducial marks and the locations of critical defectsdetected with a highly sensitive defect inspection apparatus aspreviously described can be managed. When fabricating the reflectivemask 40 based on the resulting critical defect location information(defect data), drawing data can be corrected and defects can be reducedso that the absorber pattern 27 is formed at those locations wherecritical defects are present based on the aforementioned defect data andtransferred pattern (circuit pattern) data.

EXAMPLES

The following provides an explanation of examples of fabricating thesubstrate with a multilayer reflective film 20 for EUV exposure, thereflective mask blank 30 and the reflective mask 40 of the presentinvention as examples thereof.

First, the multilayer reflective film 21 was deposited on the surface ofthe mask blank substrate 10 for EUV exposure in the manner describedbelow to fabricate the substrate with a multilayer reflective film 20 ofExamples 1 and 2 and Comparative Example 1.

<Fabrication of Mask Blank Substrates of Example 1 and ComparativeExample 1>

The mask blank substrate used in Example 1 and Comparative Example 1 wasfabricated in the manner described below.

An SiO₂—TiO₂-based glass substrate having a size of 152 mm×152 mm and athickness of 6.35 mm was prepared for use as the mask blank substrate10, and the front and back surfaces of the glass substrate weresequentially polished with cerium oxide abrasive particles and colloidalsilica abrasive particles using a double-sided polishing apparatusfollowed by treating the surfaces with a low concentration ofhydrofluorosilicic acid. Measurement of the surface roughness of theresulting glass substrate surface with an atomic force microscopeyielded a root mean square roughness (RMS) of 0.5 nm.

The surface morphology (surface form, flatness) and total thicknessvariation (TTV) of regions measuring 148 mm×148 mm on the front and backsurfaces of the glass substrate were measured with a wavelength-shiftinginterferometer using a wavelength-modulating laser. As a result, theflatness of the front and back surfaces of the glass substrate was 290nm (convex shape). The results of measuring the surface morphology(flatness) of the glass substrate surface were stored in a computer inthe form of height information with respect to a reference surface foreach measurement point, compared with a reference value of 50 nm (convexshape) for the flatness of the front surface and a reference value of 50nm for the flatness of the back surface required by glass substrates,and the differences therewith (required removal amounts) were calculatedby computer.

Next, processing conditions for local surface processing were setcorresponding to the required removal amounts for each processingspot-shaped region on the surface of the glass substrate. A dummysubstrate was used and preliminarily processed at a spot in the samemanner as actual processing without moving the substrate for a fixedperiod of time, the morphology thereof was measured with the samemeasuring instrument as the apparatus used to measure the surfacemorphology of the aforementioned front and back surfaces, and theprocessing volume of the spot was measured per unit time. The scanningspeed during Raster scanning of the glass substrate was then determinedin accordance with the required removal amount obtained from the spotinformation and surface morphology information of the glass substrate.

Surface morphology was adjusted by carrying out local surface processingtreatment in accordance with the set processing conditions bymagnetorheological finishing (MRF) using a substrate finishing apparatusemploying a magnetorheological fluid so that the flatness of the frontand back surfaces of the glass substrate was not more than theaforementioned reference values. Furthermore, the magnetorheologicalfluid used at this time contained an iron component, and the polishingslurry used an alkaline aqueous solution containing about 2% by weightof an abrasive in the form of cerium oxide. Subsequently, the glasssubstrate was immersed in a cleaning tank containing an aqueoushydrochloric acid solution having a concentration of about 10%(temperature: about 25′C) for about 10 minutes followed by rinsing withpure water and drying with isopropyl alcohol (IPA).

Measurement of the surface morphology (surface form, flatness) of theresulting glass substrate surface yielded flatness for the front andback surfaces of about 40 nm to 50 nm. In addition, when surfaceroughness of the glass substrate surface was measured using an atomicforce microscope in a region measuring 1 μm×1 μm at an arbitrarylocation of the transfer pattern formation region (132 mm×132 mm), rootmean square roughness (RMS) was 0.37 nm, indicating a rough stateattributable to surface roughness prior to local surface processing byMRF.

Consequently, double-sided polishing was carried out on the front andback surfaces of the glass substrate using a double-sided polishingapparatus under polishing conditions that maintain or improve thesurface morphology of the glass substrate surface. Finishing polishingwas carried out under the polishing conditions indicated below.

-   -   Machining fluid: Aqueous alkaline solution (NaOH)+abrasive        (concentration: about 2% by weight)    -   Abrasive: Colloidal silica, mean particle diameter: about 70 nm    -   Polishing surface plate rotating speed: About 1 rpm to 50 rpm    -   Processing pressure: About 0.1 kPa to 10 kPa    -   Processing time: About 1 minute to 10 minutes

Subsequently, the glass substrate was cleaned with an aqueous alkalinesolution (NaOH) to obtain the mask blank substrate 10 for EUV exposure.

When the flatness and surface roughness of the front and back surfacesof the resulting mask blank substrate 10 were measured, the flatness onthe front and back surfaces was about 40 nm, indicating that the stateprior to processing with the double-sided polishing apparatus wasfavorably maintained or improved. In addition, when a 1 μm×1 μm regionat an arbitrary location of the transfer pattern formation region (132mm×132 mm) of the resulting mask blank substrate 10 was measured with anatomic force microscope, root mean square roughness (RMS) was 0.145 nmand maximum height (Rmax) was 1.4 nm. In addition, the maximum value ofpower spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹was 5.94 nm⁴, and the integrated value I of power spectrum density (PSD)at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ was 42.84×10⁻³ nm³. Inaddition, the maximum value of power spectrum density (PSD) at a spatialfrequency of 10 μm⁻¹ to 100 μm⁻¹ was 3.49 nm⁴, and the integrated valueI of power spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to100 μm⁻¹ was 106.96×10⁻³ nm³.

Moreover, when the resulting mask blank substrate 10 was measured withan atomic force microscope in a region measuring 3 μm×3 μm at anarbitrary location of the transfer pattern formation region (132 mm×132mm), the maximum value of power spectrum density (PSD) at a spatialfrequency of 1 μm⁻¹ to 10 μm⁻¹ was 20.41 nm⁴, and the integrated value Iof power spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10μm⁻¹ was 93.72×10⁻³ nm³.

Furthermore, the local processing method used for the mask blanksubstrate 10 in the present invention is not limited to theaforementioned magnetorheological finishing. A processing method usinggas cluster ion beams (GCIB) or localized plasma may also be used.

The mask blank substrates 10 used in Example 1 and Comparative Example 1were fabricated in the manner described above.

<Fabrication of Mask Blank Substrate of Example 2>

The mask blank substrate 10 used in Example 2 was fabricated in themanner indicated below.

Surface processing by catalyst-referred etching (CARE) was carried outon the front and back surfaces of the glass substrate for the purpose offurther decreasing the PSD of a high spatial frequency region (not lessthan 1 μm⁻¹) for the mask blank substrate 10 obtained according to thepreviously described fabrication method of Example 1. A schematicdiagram of the CARE processing apparatus used is shown in FIG. 9.Furthermore, processing conditions were as indicated below.

Machining fluid: Pure water

Catalyst: Pt

Substrate rotating speed: 10.3 rpm

Catalyst surface plate rotating speed: 10 rpm

Processing time: 50 minutes

Processing pressure: 250 hPa

Subsequently, after scrubbing the edge faces of the glass substrate, theglass substrate was immersed in a cleaning tank containing aqua regia(temperature: about 65° C.) for about 10 minutes followed by rinsingwith pure water and drying. Furthermore, cleaning with aqua regia wascarried out several times until there was no longer any Pt catalystresidue on the front and back surfaces of the glass substrate.

When a 1 μm×1 μm region at an arbitrary location of the transfer patternformation region (132 mm×132 mm) of the resulting mask blank substrate10 was measured with an atomic force microscope, the surface roughnessthereof was such that root mean square roughness (RMS) was 0.081 nm andmaximum height (Rmax) was 0.8 nm. In addition, the maximum value ofpower spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹was 4.93 nm⁴, and the integrated value I of power spectrum density (PSD)at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ was 29.26×10⁻³ nm³. Inaddition, the maximum value of power spectrum density (PSD) at a spatialfrequency of 10 μm⁻¹ to 100 μm⁻¹ was 1.91 nm⁴, and the integrated valueI of power spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to100 μm⁻¹ was 68.99×10⁻³ nm³.

Moreover, when the resulting mask blank substrate 10 was measured withan atomic force microscope in a region measuring 3 μm×3 μm at anarbitrary location of the transfer pattern formation region (132 mm×132mm), the maximum value of power spectrum density (PSD) at a spatialfrequency of 1 μm⁻¹ to 10 μm⁻¹ was 23.03 nm⁴, and the integrated value Iof power spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10μm⁻¹ was 61.81×10⁻³ nm³.

As indicated by these results, surface processing by CARE made itpossible to reduce surface roughness in a high spatial frequency region.In addition, root mean square roughness (RMS) at a spatial frequency of10 μm⁻¹ to 100 μm⁻¹ was favorable at 0.08 nm.

The mask blank substrate 10 used in Examples 2 and 3 was fabricated inthe manner described above.

<Fabrication of Multilayer Reflective Films of Examples 1 and 2>

Deposition of the multilayer reflective film 21 of Examples 1 and 2 wascarried out in the manner indicated below. Namely, a Mo layer (lowrefractive index layer, thickness: 2.8 nm) and a Si layer (highrefractive index layer, thickness: 4.2 nm) were alternately laminated byion beam sputtering (number of laminated pairs: 40) to form themultilayer reflective film 21 on the aforementioned glass substrate.During deposition of the multilayer reflective film 21 by ion beamsputtering, the incident angle of sputtered Mo and Si particles relativeto the normal of a main surface of the glass substrate in ion beamsputtering was 30 degrees and ion source gas flow rate was 8 sccm.

After depositing the multilayer reflective film 21, an Ru protectivefilm 22 (film thickness: 2.5 nm) was deposited by ion beam sputtering onthe multilayer reflective film 21 in continuation therefrom to obtainthe substrate with the substrate with a multilayer reflective film 20.When depositing the Ru protective film 22 by ion beam sputtering, theincident angle of Ru sputtered particles relative to the normal of amain surface of the substrate was 40 degrees and the ion source gas flowrate was 8 sccm.

<Fabrication of Multilayer Reflective Film of Comparative Example 1>

Deposition of the multilayer reflective film 21 of Comparative Example 1was carried out in the manner indicated below. Namely, a Mo layer(thickness: 2.8 nm) and a Si layer (thickness: 4.2 nm) were alternatelylaminated by ion beam sputtering using a Mo target and Si target (numberof laminated pairs: 40) to form the multilayer reflective film 21 on theaforementioned glass substrate. The incident angle of sputtered Mo andSi particles relative to the normal of the glass substrate in ion beamsputtering was 50 degrees for Mo and 40 degrees for Si, respectively,and ion source gas flow rate was 8 sccm. Moreover, a Ru protective film22 (film thickness: 2.5 nm) was deposited on the multilayer reflectivefilm 21 to obtain the substrate with a multilayer reflective film 20.

After depositing the multilayer reflective film 21 in the same manner asExamples 1 and 2, an Ru protective film 22 (film thickness: 2.5 nm) wasdeposited by ion beam sputtering on the multilayer reflective film 21 incontinuation therefrom to obtain the substrate with the substrate with amultilayer reflective film 20. When depositing the Ru protective film 22by ion beam sputtering, the incident angle of Ru sputtered particlesrelative to the normal of a main surface of the substrate was 40 degreesand the ion source gas flow rate was 8 sccm.

<Measurement with Atomic Force Microscope>

Regions measuring 1 μm×1 μm and 3 μm×3 μm at arbitrary locations in thetransfer pattern formation region (and more specifically, in the centerof the transfer pattern formation region, 132 mm×132 mm) were measuredwith an atomic force microscope on the surfaces of the substrates with amultilayer reflective film 20 obtained in Examples 1 and 2 andComparative Example 1. Tables 1 and 2 indicate surface roughness (rootmean square roughness, RMS) obtained by measuring with an atomic threemicroscope, and the maximum and minimum values of power spectrum density(PSD) over a prescribed spatial frequency range as determined by powerspectrum analysis of surface roughness. Moreover, Table 1 indicates theintegrated value I of power spectrum density (PSD) at a spatialfrequency of 10 μm⁻¹ to 100 μm⁻¹ when using a 1 μm×1 μm region for themeasured region. In addition, Table 2 indicates the integrated value Iof power spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10μm⁻¹ and a spatial frequency of 1 μm⁻¹ to 5 μm⁻¹ when using a 3 μm×3 μmregion for the measured region.

TABLE 1 Comparative Example 1 Example 2 Example 1 AFM Measured Region 1μm × 1 μm 1 μm × 1 μm 1 μm × 1 μm PSD Spatial frequency Maximum value(nm⁴) 13.74 20.11 23.78 1 μm⁻¹ to 10 μm⁻¹ Minimum value (nm⁴) 3.81 7.406.92 Spatial frequency Maximum value (nm⁴) 6.22 7.54 9.20 10 μm⁻¹ to 100μm⁻¹ Minimum value (nm⁴) 0.31 0.32 0.34 Integrated value I Integratedregion: 125.21 144.95 183.09 (×10⁻³ nm³) 10 μm⁻¹ to 100 μm⁻¹ RMS (nm)0.117 0.134 0.173 No. of defects detected 1240 576 58323

TABLE 2 Comparative Example 1 Example 2 Example 1 AFM Measured Region 3μm × 3 μm 3 μm × 3 μm 3 μm × 3 μm PSD Spatial frequency Maximum value(nm⁴) 36.34 32.40 55.66 1 μm⁻¹ to 10 μm⁻¹ Minimum value (nm⁴) 12.09 8.7912.40 Integrated value I Integrated region: 163.12 150.51 193.82 (×10⁻³nm³) 1 μm⁻¹ to 10 μm⁻¹ Integrated region: 101.43 93.27 117.25 1 μm⁻¹ to5 μm⁻¹ RMS (nm) 0.126 0.130 0.170 No. of defects detected 1240 576 58323

For reference purposes, FIGS. 5 and 6 indicate the results of analyzingthe power spectra of Example 1 and Comparative Example 1. FIGS. 5 and 6indicate the power spectrum density (PSD) at each spatial frequencyobtained by measuring regions measuring 1 μm×1 μm and 3 μm×3 μm,respectively, with an atomic force microscope. In addition, FIG. 8indicates the results of subjecting the data shown in FIG. 5corresponding to a spatial frequency of 10 μm⁻¹ to 100 μm⁻¹ to powerapproximation. In addition, FIG. 7 indicates the results of subjectingthe data shown in FIG. 6 corresponding to a spatial frequency of 1 μm⁻¹to 10 μm⁻¹ to power approximation. The power approximation curves are inthe form of y=a·x^(b) (wherein, a and b are constants), and becomes astraight line on a double-logarithmic graph. On a double-logarithmicgraph, the exponent b of x is the slope of a straight line correspondingto the power approximation curve.

As shown in Table 1, the integrated value I of power spectrum density(PSD) at a spatial frequency of 10 μm⁻¹ to 100 μm⁻¹ obtained bymeasuring a 1 μm×1 μm region of the surface of the substrate with amultilayer reflective film 20 of Examples 1 and 2 with an atomic forcemicroscope was not more than 150×10⁻³ nm³, and the maximum value ofpower spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to 100μm⁻¹ was not more than 9 nm⁴. In contrast, the integrated value I ofpower spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to 100μm⁻¹ obtained by measuring a 1 μm×1 μm region of the surface of thesubstrate with a multilayer reflective film 20 of Comparative Example 1with an atomic force microscope was 183.09×10⁻³ nm³, and the maximumvalue of power spectrum density (PSD) at a spatial frequency of 10 μm⁻¹to 100 μm⁻¹ was 9.2 nm⁴.

As shown in FIG. 8, the value of b, which is the slope of the powerapproximation curve (straight line) of the aforementioned power spectrumdensity at a spatial frequency of 10 μm⁻¹ to 100 μm⁻¹ obtained bymeasuring a 1 μm×1 μm region of Example 1 with an atomic forcemicroscope, is a negative value. Thus, the power spectrum density (PSD)at a spatial frequency of 10 μm⁻¹ to 100 μm⁻¹ obtained by measuring a 1μm×1 μm region of Example 1 with an atomic force microscope clearly hasthe characteristic of an overall monotonic decrease.

As shown in Table 2, the integrated value I of power spectrum density(PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ obtained by measuringa 3 μm×3 μm region of the surface of the substrate with a multilayerreflective film 20 of Examples 1 and 2 with an atomic force microscopewas not more than 180×10⁻³ nm³, and the maximum value of power spectrumdensity (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ was not morethan 50 nm⁴. In contrast, the integrated value I of power spectrumdensity (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ obtained bymeasuring a 3 μm×3 μm region of the surface of the substrate with amultilayer reflective film 20 of Comparative Example 1 with an atomicforce microscope was 193.82×10⁻³ nm³, and the maximum value of powerspectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ was55.66 nm⁴.

As shown in FIG. 7, the value of b, which is the slope of the powerapproximation curve (straight line) of the aforementioned power spectrumdensity at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ obtained bymeasuring a 3 μm×3 μm region of Example 1 with an atomic forcemicroscope, is a negative value. Thus, the power spectrum density (PSD)at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ obtained by measuring a 3μm×3 μm region of Example 1 with an atomic force microscope clearly hasthe characteristic of an overall monotonic decrease.

Regions measuring 132 mm×132 min on the surface of the substrate with amultilayer reflective film 20 of Examples 1 and 2 and ComparativeExample 1 (surface of Ru protective film 22) were inspected for defectsunder inspection sensitivity conditions enabling detection of defectshaving a sphere equivalent volume diameter (SEVD) of 21.5 nm using ahighly sensitive defect inspection apparatus having an inspection lightsource wavelength of 193 nm (“Teron 610” manufactured by KLA-TencorCorp.). Furthermore, sphere equivalent volume diameter (SEVD) can becalculated according to the equation: SEVD=2(3S/4πh)^(1/3), where (S) isdefined as the defect area and (h) is defined as the defect height. Thedefect area (S) and defect height (h) can be measured with an atomicforce microscope (AFM).

Tables 1 and 2 indicate the number of defects detected, including pseudodefects, in the surface of the substrates with a multilayer reflectivefilm 20 of Examples 1 and 2 and Comparative Example 1 as determined bymeasuring SEVD. The maximum total number of defects detected in Examples1 and 2 was 1,240 (Example 1), indicating that the number of pseudodefects was significantly inhibited in comparison with the more than50,000 detects conventionally detected. A total of about 2,000 detecteddefects means that the presence or absence of contaminants, scratchesand other critical defects can be inspected easily. In contrast, thenumber of defects detected in Comparative Example 1 was 58,323,indicating that inspections were unable to be carried out for thepresence or absence of contaminants, scratches or other criticaldefects.

Moreover, the number of detects, including pseudo defects, detected wasinvestigated when defect inspections were carried out under differentinspection sensitivity conditions on the surface of the substrates witha multilayer reflective film 20 of Examples 1 and 2 and ComparativeExample 1. Those results are shown in Table 3.

TABLE 3 Inspection sensitivity Comparative conditions Example 1 Example2 Example 1 No. of defects >21 nm 1240 576 58323 detected >23 nm 89 5215211 >25 nm 48 34 98 >34 nm 16 9 31

Furthermore, the inspection sensitivity conditions shown in Table 3represent sensitivity conditions enabling inspection for defects havinga size of 21.5 nm in terms of SEVD (>21 nm), sensitivity conditionsenabling inspection for defects having a size of 23 nm (>23 nm),sensitivity conditions enabling inspection for defects having a size of25 nm (>25 nm), and sensitivity conditions enabling inspection fordefects having a size of 34 nm (>34 nm).

As shown in Table 3, the number of defects detected in Examples 1 and 2was not more than 100 under any of the sensitivity conditions enablinginspection for detects having a size of 23 nm, 25 nm or 34 nm, and thepresence or absence of contaminants, scratches or other critical defectswas able to be easily inspected. In contrast, because the number ofdefects detected exceeded 50,000 in Comparative Example 1 undersensitivity conditions enabling inspection for defects having a size of21.5 nm and exceeded 15,000 under sensitivity conditions enablinginspection for defects having a size of 23 nm, it was difficult toinspect for the presence or absence of contaminants, scratches or othercritical defects at multiple inspection sensitivities.

In addition, as a result of inspecting regions measuring 132 mm×132 mmon the surface of the multilayer reflective film 21 of Examples 1 and 2for detects using a highly sensitive defect inspection apparatus havingan inspection light source wavelength of 266 nm (“MAGICS M7360”manufactured by Lasertec Corp.) and a highly sensitive defect inspectionapparatus having an inspection light source wavelength of 13.5 nm, therewere few defects detected and it was possible to inspect for criticaldefects. Furthermore, defect inspections were carried out under themaximum inspection sensitivity conditions when using the highlysensitive defect inspection apparatus having an inspection light sourcewavelength of 266 nm (“MAGICS M7360” manufactured by Lasertec Corp.),and under inspection sensitivity conditions enabling detection ofdefects having a sphere equivalent volume diameter of 20 nm when usingthe highly sensitive defect inspection apparatus having an inspectionlight source wavelength of 13.5 nm.

Furthermore, fiducial marks for managing coordinates of the locations ofthe aforementioned defects were formed with a focused ion beam at 4locations outside the transfer pattern formation region (132 mm×132 mm)on the protective film 22 and the multilayer reflective film 21 of thesubstrates with a multilayer reflective film 20 used in Examples 1 and 2and Comparative Example 1.

<Fabrication of Reflective Mask Blanks 30 for EUV Exposure of Examples 1and 2 and Comparative Example 1>

The back side electrically conductive film 23 was formed by DC magnetronsputtering on the back side of the substrate with a multilayerreflective film 20 of the previously described Examples 1 and 2 andComparative Example 1 where the multilayer reflective film 21 was notformed. This back side electrically conductive film 23 was formed byreactive sputtering in an atmosphere of Ar gas and N₂ gas(Ar:N₂=90%:10%) with a Cr target opposing the back side of the substratewith a multilayer reflective film 20. Measurement of the elementarycomposition of the back side electrically conductive film 23 byRutherford back scattering analysis yielded values of 90 at % for Cr and10 at % for N. In addition, the film thickness of the back sideelectrically conductive film 23 was 20 nm.

Moreover, the absorber film 24 composed of a TaBN film was formed by DCmagnetron sputtering on the surface of the protective film 22 of thesubstrate with a multilayer reflective film 20 of the aforementionedExamples 1 and 2 and Comparative Example 1 to fabricate the reflectivemask blank 30. The absorber film 24 was formed by reactive sputtering inan atmosphere of Xe gas and N₂ gas (Xe:N₂=90%:10%) with the protectivefilm 22 of the substrate with a multilayer reflective film 20 opposing aTaB target (Ta:B=80:20, atomic ratio). Measurement of the elementarycomposition of the absorber film 24 by Rutherford back scatteringanalysis yielded values of 0.80 at % for Ta, 10 at % for B and 10 at %for N. In addition, the film thickness of the absorber film 24 was 65nm. Furthermore, measurement of the crystal structure of the absorberfilm 24 with an X-ray diffraction (XRD) analyzer indicated it to have anamorphous structure.

When the surface of the reflective mask blank 30 obtained according tothe aforementioned fabrication method was inspected for defects (“MAGICS1350” manufactured by Lasertec Corp.), only three defects were detected,indicating that a favorable reflective mask blank was obtained.

<Fabrication of Reflective Mask Blanks 30 of Examples 3 and 4 andComparative Example 2>

The reflective mask blanks 30 of Examples 3 and 4 were fabricated bydepositing the absorber films 24 shown in Table 4 on the surface of thesubstrate with a multilayer reflective film 20 (surface of Ru protectivefilm 22) of the aforementioned Example 2. More specifically, theabsorber film 24 was formed by laminating a tantalum nitride film (TaNfilm) and a chromium carboxonitride film (CrCON film) by DC sputtering.The TaN films were formed in the manner indicated below. Namely, TaNfilms (Ta: 85 at %, N: 15 at %) having the film thicknesses described inTable 4 were formed by reactive sputtering in a mixed gas atmosphere ofAr gas and N₂ gas using a tantalum target. The CrCON films were formedin the manner indicated below. Namely, CrCON films (Cr: 45 at %, C: 10at %, O: 35 at %, N: 10 at %) having the film thicknesses described inTable 4 were formed by reactive sputtering in a mixed gas atmosphere ofAr gas, CO₂ gas and N₂ gas using a chromium target. Moreover, similar toExample 2, the reflective mask blanks 30 of Examples 3 and 4 werefabricated by depositing the back side electrically conductive film 23on the back side of the mask blank substrate 10.

On the other hand, the reflective mask blank 30 of Comparative Example 2was fabricated by depositing the absorber films 24 shown in Table 4 onthe surface (surface of Ru protective film 22) of the substrate with amultilayer reflective film 20 of the aforementioned Example 2. Morespecifically, TaN films (Ta: 92 at %, N: 8 at %) having the filmthicknesses described in Table 4 were formed by reactive sputtering in amixed gas atmosphere of Ar gas and N₂ gas using a tantalum target by DCsputtering.

Regions measuring 3 μm×3 μm at an arbitrary location (and morespecifically, in the center of the transfer pattern formation region) ofthe transfer pattern formation region (132 mm×132 min) were measuredwith an atomic force microscope for the surface (surface of the absorberfilm 24) of the reflective mask blanks 30 of Examples 3 and 4 andComparative Example 2. Table 4 indicates the maximum values of surfaceroughness (root mean square roughness: RMS) obtained by measuring withan atomic force microscope, power spectrum density (PSD) at a spatialfrequency of 1 μm⁻¹ to 10 μm⁻¹ as determined by power spectrum analysisof surface roughness, and the integrated value I of power spectrumdensity (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹.

TABLE 4 Comparative Example 3 Example 4 Example 2 Absorber film lowerlayer TaN TaN TaN (film thickness) (54.3 nm) (48.9 nm) (85 nm) Absorberfilm upper layer CrCON CrCON — (film thickness) (5 nm) (10 nm) Absorberfilm total 59.3 58.9 85 thickness (nm) RMS (nm) 0.24 0.24 0.46 Maximumvalue of PSD 28.9 44.4 52.1 (nm⁴) Integrated value of PSD 433.2 467.9939.5 (×10⁻³ nm³)

As shown in Table 4, the integrated values I of power spectrum density(PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ obtained by measuringa region measuring 3 μm×3 μm on the surface of the reflective maskblanks 30 of Examples 3 and 4 with an atomic force microscope were notmore than 800×10⁻³ nm³ (and more specifically, not more than 500×10⁻³nm³), and the maximum values of power spectrum density (PSD) at aspatial frequency of 1 μm⁻¹ to 10 μm⁻¹ were not more than 50 nm⁴. Incontrast, the integrated value I of power spectrum density (PSD) at aspatial frequency of 1 μm⁻¹ to 10 μm⁻¹ obtained by measuring a regionmeasuring 3 μm×3 μm on the surface of the reflective mask blank 30 ofComparative Example 2 with an atomic force microscope exceeded 800×10⁻³nm³ at 939.5×10⁻³ nm³, and the maximum value of power spectrum density(PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ exceeded 50 nm⁴ at52.1 nm⁴.

Next, the number of defects, including pseudo defects, detected wasinvestigated when defect inspections were carried out on the surface ofthe reflective mask blanks 30 of Examples 3 and 4 and ComparativeExample 2 under different inspection sensitivity conditions. The resultsare shown in Table 5.

TABLE 5 Inspection sensitivity Comparative conditions Example 3 Example4 Example 2 No. of defects >21 nm 6254 10094 69950 detected >23 nm 23185001 23144 >25 nm 82 112 220 >34 nm 28 37 65

Furthermore, the inspection sensitivity conditions shown in Table 5represent sensitivity conditions enabling inspection for defects havinga size of 21.5 nm in terms of sphere equivalent volume diameter (SEVD)(>21 nm), sensitivity conditions enabling inspection for defects havinga size of 23 nm (>23 nm), sensitivity conditions enabling inspection fordefects having a size of 25 nm (>25 nm), and sensitivity conditionsenabling inspection for defects having a size of 34 nm (>34 nm).

As shown in Table 5, the number of defects detected in Examples 3 and 4was not more than 15,000 under any of the sensitivity conditionsenabling inspection for detects having a size of 23 nm, 25 nm or 34 nm,and the presence or absence of contaminants, scratches or other criticaldefects was able to be easily inspected. In contrast, because the numberof defects detected exceeded 50,000 in Comparative Example 2 undersensitivity conditions enabling inspection for defects having a size of21.5 nm and exceeded 20,000 under sensitivity conditions enablinginspection for defects having a size of 23 nm, it was difficult toinspect for the presence or absence of contaminants, scratches or othercritical defects.

<Fabrication of Reflective Mask 40>

The surface of the absorber film 24 of the reflective mask blanks 30 ofExamples 1 to 4 and Comparative Examples 1 and 2 was coated with resistby spin coating and a resist film having a film thickness of 150 nm wasdeposited thereon after going through heating and cooling steps. Next, aresist pattern was formed by going through desired pattern drawing anddeveloping steps. The absorber film 24 was patterned by a prescribed dryetching using the resist pattern as a mask to thrill the absorberpattern 27 on the protective film 22. Furthermore, when the absorberfilm 24 consists of a TaBN film and TaN film, dry etching can be carriedout with a mixed gas of Cl₂ and He. In addition, when the absorber film24 consists of a CrCON film, dry etching can be carried out with a mixedgas of chlorine (Cl₂) and oxygen (O₂) (mixing ratio (flow rate ratio) ofchlorine (Cl₂) to oxygen (O₂)=8:2).

Subsequently, the resist film was removed followed by chemical cleaningin the same manner as previously described to fabricate the reflectivemasks 40 of Examples 1 to 4 and Comparative Examples 1 and 2.Furthermore, the reflective masks 40 were fabricated after correctingdrawing data in the aforementioned drawing step so that the absorberpattern 27 was arranged at locations where critical defects are presentbased on defect data and transferred pattern (circuit pattern) datagenerated based on the aforementioned fiduciary marks. Defectinspections were carried out on the resulting reflective masks 40 ofExamples 1 to 4 and Comparative Examples 1 and 2 using a highlysensitive defect inspection apparatus (“Teron 610” manufactured byKLA-Tencor Corp.).

Defects were not confirmed during measurement with the highly sensitivedefect inspection apparatus in the case of the reflective masks 40 ofExamples 1 to 4. In contrast, in the case of the reflective masks 40 ofComparative Examples 1 and 2, a large number of defects were detectedduring measurement with the highly sensitive defect inspectionapparatus.

<Method of Manufacturing Semiconductor Device>

Next, when semiconductor devices were fabricated using the reflectivemasks 40 of the aforementioned Examples 1 to 4 and carrying out patterntransfer on a resist film on a transferred substrate in the form of asemiconductor substrate using an exposure apparatus followed bypatterning an interconnection layer, semiconductor devices were able tobe fabricated that were free of pattern defects.

Furthermore, in fabricating the above described substrate with amultilayer reflective film 20 and the reflective mask blank 30, althoughthe multilayer reflective film 21 and the protective film 22 weredeposited on a main surface of the mask blank substrate 10 on the sidewhere a transfer pattern is formed, followed by forming the back sideelectrically conductive film 23 on the opposite side from theaforementioned main surface, fabrication is not limited to thissequence. The reflective mask blank 30 may also be fabricated by formingthe back side electrically conductive film 23 on a main surface of themask blank substrate 10 on the opposite side from the main surface onthe side on which a transfer pattern is formed, followed by depositingthe multilayer reflective film 21 and the protective film 22 on the mainsurface on the side where the transfer pattern is formed. In this case,the substrate with a multilayer reflective film 20 can be fabricated byfurther depositing the protective film 22 on the surface of themultilayer reflective film 21. Moreover, the reflective mask blank 30can be fabricated by depositing the absorber film 24 on the multilayerreflective film 21 or the protective film 22 of the substrate with amultilayer reflective film 20.

BRIEF DESCRIPTION OF REFERENCE SYMBOLS

-   -   10 Mask blank substrate    -   20 Substrate with a multilayer reflective film    -   21 Multilayer reflective film    -   22 Protective film    -   23 Back side electrically conductive film    -   24 Absorber film    -   27 Absorber pattern    -   30 Reflective mask blank    -   40 Reflective mask    -   100 CARE processing apparatus    -   124 Treatment tank    -   126 Catalyst surface plate    -   128 Glass substrate (processing target)    -   130 Substrate holder    -   132 Rotating shaft    -   140 Base    -   142 Platinum    -   170 Heater    -   172 Heat exchanger    -   174 Treatment liquid supply nozzle    -   176 Fluid flow path

The invention claimed is:
 1. A substrate with a multilayer reflectivefilm, comprising: a multilayer reflective film obtained by alternatelylaminating a high refractive index layer and a low refractive indexlayer on or above a main surface of a mask blank substrate used inlithography; wherein, an integrated value I of the power spectrumdensity (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ of the surfaceof the substrate with a multilayer reflective film, obtained bymeasuring a region measuring 3 μm×3μm with an atomic force microscope,is not more than 180×10⁻³ nm³, and the maximum value of the powerspectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ isnot more than 50 nm⁴.
 2. The substrate with a multilayer reflective filmaccording to claim 1, wherein an integrated value I of the powerspectrum density (PSD) at a spatial frequency of 1μm⁻¹ to 5 μm⁻¹ of thesurface of the substrate with a multilayer reflective film, obtained bymeasuring a region measuring 3 μm×3 μm with an atomic force microscope,is not more than 115×10⁻³ nm³.
 3. The substrate with a multilayerreflective film according to claim 1, wherein the power spectrum densityat a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ has the characteristic of anoverall monotonic decrease.
 4. The substrate with a multilayerreflective film according to claim 1, wherein a protective film isprovided on or above the multilayer reflective film.
 5. A reflectivemask blank, comprising: an absorber film serving as a transfer patternon or above the multilayer reflective film of the substrate with amultilayer reflective film according to claim
 1. 6. A reflective mask,comprising: an absorber pattern on or above the multilayer reflectivefilm by patterning the absorber film in the reflective mask blankaccording to claim
 5. 7. A method of manufacturing a semiconductordevice comprising forming a transfer pattern on or above a transferredsubstrate by carrying out a lithography process with an exposureapparatus using the reflective mask according to claim
 6. 8. A substratewith a multilayer reflective film, comprising: a multilayer reflectivefilm obtained by alternately laminating a high refractive index layerand a low refractive index layer on or above a main surface of a maskblank substrate used in lithography; wherein, an integrated value I ofthe power spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to100 μm⁻¹ of the surface of the substrate with a multilayer reflectivefilm, obtained by measuring a region measuring 1 μm×1μm with an atomicforce microscope, is not more than 150×10⁻³ nm³, and the maximum valueof the power spectrum density (PSD) at a spatial frequency of 10 μm⁻¹ to100 μm⁻¹ is not more than 9 nm⁴.
 9. The substrate with a multilayerreflective film according to claim 8, wherein the power spectrum densityat a spatial frequency of 10 μm⁻¹ to 100 μm⁻¹ has the characteristic ofan overall monotonic decrease.
 10. The substrate with a multilayerreflective film according to claim 8, wherein a protective film isprovided on or above the multilayer reflective film.
 11. A reflectivemask blank, comprising: an absorber film serving as a transfer patternon or above the multilayer reflective film of the substrate with amultilayer reflective film according to claim
 8. 12. A reflective maskblank, comprising: a multilayer reflective film, obtained by alternatelylaminating a high refractive index layer and a low refractive indexlayer on or above a main surface of a mask blank substrate used inlithography, and an absorber film; wherein, an integrated value I of thepower spectrum density (PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ of the surface of the absorber film, obtained by measuring a regionmeasuring 3 μm×3 μm with an atomic force microscope, is not more than800×10 ⁻³ nm ³ , and the maximum value of the power spectrum density(PSD) at a spatial frequency of 1 μm⁻¹ to 10 μm⁻¹ is not more than 50nm⁴.
 13. A reflective mask, comprising: an absorber pattern on or abovethe multilayer reflective film by patterning the absorber film in thereflective mask blank according to claim
 12. 14. A reflective mask,comprising: an absorber pattern on or above the multilayer reflectivefilm by patterning the absorber film in the reflective mask blankaccording to claim 13.